Post on 03-Jun-2020
Acyclic 12-Dimagnesioethanes-ethene Derived from Magnesium(I)
Compounds Multipurpose Reagents for Organometallic Synthesis
Deepak Dangea Andrew R Gairab Dafydd D L Jonesa Martin Juckela Simon Aldridgeb and
Cameron Jonesa
a School of Chemistry PO Box 23 Monash University VIC 3800 Australia
b Inorganic Chemistry Laboratory Department of Chemistry University of Oxford South Parks
Road Oxford OX1 3QR UK
Supplementary Information (30 pages)
Contents 1 Experimental S2
2 X-Ray Crystallography S25
3 References S29
S 1
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is copy The Royal Society of Chemistry 2019
1 Experimental
General considerations
All manipulations were carried out using standard Schlenk and glove box techniques under an
atmosphere of high purity dinitrogen Pentane was distilled over NaK alloy (2575) while THF
hexane and toluene were distilled over molten potassium 1H 13C1H 29Si1H and 11B1H NMR
spectra were recorded on either Bruker DPX300 or Bruker AvanceIII 400 spectrometers and were
referenced to the resonances of the solvent used external SiMe4 or external BF3OEt2 Mass spectra
were recorded on an Agilent Technologies 5975D inert MSD with a solid state probe IR spectra
were recorded as Nujol mulls using a Agilent Cary 630 spectrometer operating in attenuated total
reflectance (ATR) or transmission modes Melting points were determined in sealed glass
capillaries under dinitrogen and are uncorrected Microanalyses were carried out at the Science
Centre London Metropolitan University The compounds [(ArNacnac)Mg2] (Ar = Xyl1 Mes2 or
Dep3) [(MesNacnac)Mg2(-DPE)]4 [LZnBr]5 [TBoLZnBr]6 K[PhBoL]7 [(LdaggerMgI)2]8 and
[LGeCl]9 were prepared by literature procedures All other reagents were used as received
Synthesis of [(XylNacnac)Mg2(-DPE)] (5) To a stirred solution of [(XylNacnac)Mg2] (040 g
0605 mmol) in toluene (60 mL) at -40 degC was added neat 11-diphenylethylene (022 mL 121
mmol) via a microsyringe The yellow solution became deep red upon addition and was then
warmed to room temperature Volatiles were removed in vacuo and the residue taken up in hexane
(ca 20 mL) and stored at -30 degC overnight yielding deep red blocks of 5 Isolation of the crystals
and further evaporation of the filtrate gave a second crop of crystals (040 g 78) NB 5 may be
cleanly prepared in situ for further reactions by the addition of one equivalent of 11-
diphenylethylene to a stirred solution of [(XylNacnac)Mg2] in toluene at room temperature Mp
97-101 degC 1H NMR (400 MHz 298 K C6D6) δ = 037 (s 2H MgCH2CPh2) 142 (s 12H
NCCH3) 186 (s 24H ArCH3) 470 (s 2H NCCH) 623-635 (m 4H ArH) 646-649 (m 2H
ArH) 674-678 (m 4H ArH) 688 (br s 12H ArH) 13C1H NMR (100 MHz 298 K C6D6) δ =
119 (CH2CPh2) 188 (NCCH3) 228 (ArCH3) 518 (CH2CPh2) 948 (NCCH) 1162 1177
1245 1285 1304 1318 1470 1474 (ArC) 1685 (NCCH3) IR νcm-1 (ATR) = 1522(s)
1474(s) 1448(s) 1145(m) 1182(s) 847(m) 761(m) 738(s) 696(s) EIMS (70eV) mz () 3291
(XylNacnacMg+ 68) anal calc for C56H62Mg2N4 C 8010 H 744 N 667 found C
8003 H752 N 670
S 2
Figure S1 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
S 3
Figure S2 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
Synthesis of [(DepNacnac)Mg2(-MS)] (6) To a stirred solution of [(DepNacnac)Mg2] (050 g
0624 mmol) in toluene (40 mL) at -40 degC was added neat -methyl styrene (016 mL 124 mmol)
via a microsyringe The yellow solution became deep red upon addition and was then warmed to
room temperature Volatiles were removed in vacuo and the residue taken up in hexane (ca 20 mL)
and stored at -30 ordmC overnight yielding deep red blocks of 6 Isolation and further evaporation of
the filtrate gave a second crop of crystals (035 g 64 ) NB 6 may be cleanly prepared in situ for
further reactions by the addition of one equivalent of -methyl styrene to a stirred solution of
[(DepNacnac)Mg2] in toluene at room temperature Mp 139-143 degC 1H NMR (400 MHz 298 K
C6D6) δ = 016 (s 2H MgCH2CPhCH3) 109-114 (m 27H CH2CH3 and CH2CPhCH3 ) 150 (s
12H NCCH3) 213 (m 8H CH2CH3) 240 (m 8H CH2CH3) 478 (s 2H NCCH) 641-646 (m
1H ArH) 677-683 (m 2H ArH) 704-707 (m 14H ArH) 13C1H NMR (100 MHz C6D6) δ =
138 (CH2CPhCH3) 144 (CH2CH3) 218 (CPhCH3) 232 (NCCH3) 252 (CH2CH3) 948
(NCCH) 1124 (CH2CPhCH3) 1249 1258 1276 1285 1370 1416 1436 1462 (ArC) 1687
(NCCH3) IR νcm-1 (ATR) = 1516(s) 1439(s) 1264(s) 1178(s) 1028(s) 978(m) 801(m) 748(s)
695(s) EIMS (70eV) mz () 1741 (MeCNDep+ 100) 3853 (DepNacnacMg+ 35) anal calc for
C59H76Mg2N4 C 7963 H 861 N 630 found C 7866 H796 N 639
S 4
Figure S3 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
S 5
Figure S4 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
Synthesis of [(MesNacnac)Mg2(-TS)] (7) [(MesNacnac)Mg2] (300 mg 0419 mmol) and trans-
stilbene (84 mg 0466 mmol) were dissolved in toluene (15mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred overnight after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of 7 (216 mg 57 ) NMR spectra of analytically
pure crystalline samples showed one other significant product in addition to 7 This is thought to be
a diastereomer which co-crystallises with 7 and cannot be separated The NMR assignments below
are only tentative Mp 130-133degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 148 (s 12H
NCCH3) 164 (broad 12H ArCH3) 208-216 (2 broad overlapping signals 24H ArCH3) 250 (s
2H MgC(Ph)H) 472 (s 2H NCCH) 649-734 (m 18H ArH) 13C1H NMR (75 MHz 298 K
C6D6) δ = 189 (ArCH3) 210 (ArCH3) 230 (NCCH3) 460 (MgCH(Ph) 950 (NCCH) 1163
1270 1289 1291 1293 1315 1331 1570 (ArC) 1682 (NCCH3) IR νcm-1 (ATR) 1654 (w)
1597 (m) 1541 (m) 1508(m) 1474 (m) 1446 (m) 1366 (s) 1313 (w) 1256 (m) 1197 (m) 1161
(m) 1106 (w) 1052 (m) 848 (w) 793 (m) 763 (m) 741 (m) 697 (s) EIMS (70eV) mz () 3573
(MesNacnacMg+ 100) anal calc for C60H70Mg2N4 C 8044 Η 788 Ν 625 found C
8032 Η 806 Ν 639
S 6
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
1 Experimental
General considerations
All manipulations were carried out using standard Schlenk and glove box techniques under an
atmosphere of high purity dinitrogen Pentane was distilled over NaK alloy (2575) while THF
hexane and toluene were distilled over molten potassium 1H 13C1H 29Si1H and 11B1H NMR
spectra were recorded on either Bruker DPX300 or Bruker AvanceIII 400 spectrometers and were
referenced to the resonances of the solvent used external SiMe4 or external BF3OEt2 Mass spectra
were recorded on an Agilent Technologies 5975D inert MSD with a solid state probe IR spectra
were recorded as Nujol mulls using a Agilent Cary 630 spectrometer operating in attenuated total
reflectance (ATR) or transmission modes Melting points were determined in sealed glass
capillaries under dinitrogen and are uncorrected Microanalyses were carried out at the Science
Centre London Metropolitan University The compounds [(ArNacnac)Mg2] (Ar = Xyl1 Mes2 or
Dep3) [(MesNacnac)Mg2(-DPE)]4 [LZnBr]5 [TBoLZnBr]6 K[PhBoL]7 [(LdaggerMgI)2]8 and
[LGeCl]9 were prepared by literature procedures All other reagents were used as received
Synthesis of [(XylNacnac)Mg2(-DPE)] (5) To a stirred solution of [(XylNacnac)Mg2] (040 g
0605 mmol) in toluene (60 mL) at -40 degC was added neat 11-diphenylethylene (022 mL 121
mmol) via a microsyringe The yellow solution became deep red upon addition and was then
warmed to room temperature Volatiles were removed in vacuo and the residue taken up in hexane
(ca 20 mL) and stored at -30 degC overnight yielding deep red blocks of 5 Isolation of the crystals
and further evaporation of the filtrate gave a second crop of crystals (040 g 78) NB 5 may be
cleanly prepared in situ for further reactions by the addition of one equivalent of 11-
diphenylethylene to a stirred solution of [(XylNacnac)Mg2] in toluene at room temperature Mp
97-101 degC 1H NMR (400 MHz 298 K C6D6) δ = 037 (s 2H MgCH2CPh2) 142 (s 12H
NCCH3) 186 (s 24H ArCH3) 470 (s 2H NCCH) 623-635 (m 4H ArH) 646-649 (m 2H
ArH) 674-678 (m 4H ArH) 688 (br s 12H ArH) 13C1H NMR (100 MHz 298 K C6D6) δ =
119 (CH2CPh2) 188 (NCCH3) 228 (ArCH3) 518 (CH2CPh2) 948 (NCCH) 1162 1177
1245 1285 1304 1318 1470 1474 (ArC) 1685 (NCCH3) IR νcm-1 (ATR) = 1522(s)
1474(s) 1448(s) 1145(m) 1182(s) 847(m) 761(m) 738(s) 696(s) EIMS (70eV) mz () 3291
(XylNacnacMg+ 68) anal calc for C56H62Mg2N4 C 8010 H 744 N 667 found C
8003 H752 N 670
S 2
Figure S1 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
S 3
Figure S2 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
Synthesis of [(DepNacnac)Mg2(-MS)] (6) To a stirred solution of [(DepNacnac)Mg2] (050 g
0624 mmol) in toluene (40 mL) at -40 degC was added neat -methyl styrene (016 mL 124 mmol)
via a microsyringe The yellow solution became deep red upon addition and was then warmed to
room temperature Volatiles were removed in vacuo and the residue taken up in hexane (ca 20 mL)
and stored at -30 ordmC overnight yielding deep red blocks of 6 Isolation and further evaporation of
the filtrate gave a second crop of crystals (035 g 64 ) NB 6 may be cleanly prepared in situ for
further reactions by the addition of one equivalent of -methyl styrene to a stirred solution of
[(DepNacnac)Mg2] in toluene at room temperature Mp 139-143 degC 1H NMR (400 MHz 298 K
C6D6) δ = 016 (s 2H MgCH2CPhCH3) 109-114 (m 27H CH2CH3 and CH2CPhCH3 ) 150 (s
12H NCCH3) 213 (m 8H CH2CH3) 240 (m 8H CH2CH3) 478 (s 2H NCCH) 641-646 (m
1H ArH) 677-683 (m 2H ArH) 704-707 (m 14H ArH) 13C1H NMR (100 MHz C6D6) δ =
138 (CH2CPhCH3) 144 (CH2CH3) 218 (CPhCH3) 232 (NCCH3) 252 (CH2CH3) 948
(NCCH) 1124 (CH2CPhCH3) 1249 1258 1276 1285 1370 1416 1436 1462 (ArC) 1687
(NCCH3) IR νcm-1 (ATR) = 1516(s) 1439(s) 1264(s) 1178(s) 1028(s) 978(m) 801(m) 748(s)
695(s) EIMS (70eV) mz () 1741 (MeCNDep+ 100) 3853 (DepNacnacMg+ 35) anal calc for
C59H76Mg2N4 C 7963 H 861 N 630 found C 7866 H796 N 639
S 4
Figure S3 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
S 5
Figure S4 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
Synthesis of [(MesNacnac)Mg2(-TS)] (7) [(MesNacnac)Mg2] (300 mg 0419 mmol) and trans-
stilbene (84 mg 0466 mmol) were dissolved in toluene (15mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred overnight after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of 7 (216 mg 57 ) NMR spectra of analytically
pure crystalline samples showed one other significant product in addition to 7 This is thought to be
a diastereomer which co-crystallises with 7 and cannot be separated The NMR assignments below
are only tentative Mp 130-133degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 148 (s 12H
NCCH3) 164 (broad 12H ArCH3) 208-216 (2 broad overlapping signals 24H ArCH3) 250 (s
2H MgC(Ph)H) 472 (s 2H NCCH) 649-734 (m 18H ArH) 13C1H NMR (75 MHz 298 K
C6D6) δ = 189 (ArCH3) 210 (ArCH3) 230 (NCCH3) 460 (MgCH(Ph) 950 (NCCH) 1163
1270 1289 1291 1293 1315 1331 1570 (ArC) 1682 (NCCH3) IR νcm-1 (ATR) 1654 (w)
1597 (m) 1541 (m) 1508(m) 1474 (m) 1446 (m) 1366 (s) 1313 (w) 1256 (m) 1197 (m) 1161
(m) 1106 (w) 1052 (m) 848 (w) 793 (m) 763 (m) 741 (m) 697 (s) EIMS (70eV) mz () 3573
(MesNacnacMg+ 100) anal calc for C60H70Mg2N4 C 8044 Η 788 Ν 625 found C
8032 Η 806 Ν 639
S 6
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S1 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
S 3
Figure S2 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
Synthesis of [(DepNacnac)Mg2(-MS)] (6) To a stirred solution of [(DepNacnac)Mg2] (050 g
0624 mmol) in toluene (40 mL) at -40 degC was added neat -methyl styrene (016 mL 124 mmol)
via a microsyringe The yellow solution became deep red upon addition and was then warmed to
room temperature Volatiles were removed in vacuo and the residue taken up in hexane (ca 20 mL)
and stored at -30 ordmC overnight yielding deep red blocks of 6 Isolation and further evaporation of
the filtrate gave a second crop of crystals (035 g 64 ) NB 6 may be cleanly prepared in situ for
further reactions by the addition of one equivalent of -methyl styrene to a stirred solution of
[(DepNacnac)Mg2] in toluene at room temperature Mp 139-143 degC 1H NMR (400 MHz 298 K
C6D6) δ = 016 (s 2H MgCH2CPhCH3) 109-114 (m 27H CH2CH3 and CH2CPhCH3 ) 150 (s
12H NCCH3) 213 (m 8H CH2CH3) 240 (m 8H CH2CH3) 478 (s 2H NCCH) 641-646 (m
1H ArH) 677-683 (m 2H ArH) 704-707 (m 14H ArH) 13C1H NMR (100 MHz C6D6) δ =
138 (CH2CPhCH3) 144 (CH2CH3) 218 (CPhCH3) 232 (NCCH3) 252 (CH2CH3) 948
(NCCH) 1124 (CH2CPhCH3) 1249 1258 1276 1285 1370 1416 1436 1462 (ArC) 1687
(NCCH3) IR νcm-1 (ATR) = 1516(s) 1439(s) 1264(s) 1178(s) 1028(s) 978(m) 801(m) 748(s)
695(s) EIMS (70eV) mz () 1741 (MeCNDep+ 100) 3853 (DepNacnacMg+ 35) anal calc for
C59H76Mg2N4 C 7963 H 861 N 630 found C 7866 H796 N 639
S 4
Figure S3 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
S 5
Figure S4 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
Synthesis of [(MesNacnac)Mg2(-TS)] (7) [(MesNacnac)Mg2] (300 mg 0419 mmol) and trans-
stilbene (84 mg 0466 mmol) were dissolved in toluene (15mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred overnight after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of 7 (216 mg 57 ) NMR spectra of analytically
pure crystalline samples showed one other significant product in addition to 7 This is thought to be
a diastereomer which co-crystallises with 7 and cannot be separated The NMR assignments below
are only tentative Mp 130-133degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 148 (s 12H
NCCH3) 164 (broad 12H ArCH3) 208-216 (2 broad overlapping signals 24H ArCH3) 250 (s
2H MgC(Ph)H) 472 (s 2H NCCH) 649-734 (m 18H ArH) 13C1H NMR (75 MHz 298 K
C6D6) δ = 189 (ArCH3) 210 (ArCH3) 230 (NCCH3) 460 (MgCH(Ph) 950 (NCCH) 1163
1270 1289 1291 1293 1315 1331 1570 (ArC) 1682 (NCCH3) IR νcm-1 (ATR) 1654 (w)
1597 (m) 1541 (m) 1508(m) 1474 (m) 1446 (m) 1366 (s) 1313 (w) 1256 (m) 1197 (m) 1161
(m) 1106 (w) 1052 (m) 848 (w) 793 (m) 763 (m) 741 (m) 697 (s) EIMS (70eV) mz () 3573
(MesNacnacMg+ 100) anal calc for C60H70Mg2N4 C 8044 Η 788 Ν 625 found C
8032 Η 806 Ν 639
S 6
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S2 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 5
[(XylNacnac)Mg2] and DPE at 298 K
Synthesis of [(DepNacnac)Mg2(-MS)] (6) To a stirred solution of [(DepNacnac)Mg2] (050 g
0624 mmol) in toluene (40 mL) at -40 degC was added neat -methyl styrene (016 mL 124 mmol)
via a microsyringe The yellow solution became deep red upon addition and was then warmed to
room temperature Volatiles were removed in vacuo and the residue taken up in hexane (ca 20 mL)
and stored at -30 ordmC overnight yielding deep red blocks of 6 Isolation and further evaporation of
the filtrate gave a second crop of crystals (035 g 64 ) NB 6 may be cleanly prepared in situ for
further reactions by the addition of one equivalent of -methyl styrene to a stirred solution of
[(DepNacnac)Mg2] in toluene at room temperature Mp 139-143 degC 1H NMR (400 MHz 298 K
C6D6) δ = 016 (s 2H MgCH2CPhCH3) 109-114 (m 27H CH2CH3 and CH2CPhCH3 ) 150 (s
12H NCCH3) 213 (m 8H CH2CH3) 240 (m 8H CH2CH3) 478 (s 2H NCCH) 641-646 (m
1H ArH) 677-683 (m 2H ArH) 704-707 (m 14H ArH) 13C1H NMR (100 MHz C6D6) δ =
138 (CH2CPhCH3) 144 (CH2CH3) 218 (CPhCH3) 232 (NCCH3) 252 (CH2CH3) 948
(NCCH) 1124 (CH2CPhCH3) 1249 1258 1276 1285 1370 1416 1436 1462 (ArC) 1687
(NCCH3) IR νcm-1 (ATR) = 1516(s) 1439(s) 1264(s) 1178(s) 1028(s) 978(m) 801(m) 748(s)
695(s) EIMS (70eV) mz () 1741 (MeCNDep+ 100) 3853 (DepNacnacMg+ 35) anal calc for
C59H76Mg2N4 C 7963 H 861 N 630 found C 7866 H796 N 639
S 4
Figure S3 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
S 5
Figure S4 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
Synthesis of [(MesNacnac)Mg2(-TS)] (7) [(MesNacnac)Mg2] (300 mg 0419 mmol) and trans-
stilbene (84 mg 0466 mmol) were dissolved in toluene (15mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred overnight after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of 7 (216 mg 57 ) NMR spectra of analytically
pure crystalline samples showed one other significant product in addition to 7 This is thought to be
a diastereomer which co-crystallises with 7 and cannot be separated The NMR assignments below
are only tentative Mp 130-133degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 148 (s 12H
NCCH3) 164 (broad 12H ArCH3) 208-216 (2 broad overlapping signals 24H ArCH3) 250 (s
2H MgC(Ph)H) 472 (s 2H NCCH) 649-734 (m 18H ArH) 13C1H NMR (75 MHz 298 K
C6D6) δ = 189 (ArCH3) 210 (ArCH3) 230 (NCCH3) 460 (MgCH(Ph) 950 (NCCH) 1163
1270 1289 1291 1293 1315 1331 1570 (ArC) 1682 (NCCH3) IR νcm-1 (ATR) 1654 (w)
1597 (m) 1541 (m) 1508(m) 1474 (m) 1446 (m) 1366 (s) 1313 (w) 1256 (m) 1197 (m) 1161
(m) 1106 (w) 1052 (m) 848 (w) 793 (m) 763 (m) 741 (m) 697 (s) EIMS (70eV) mz () 3573
(MesNacnacMg+ 100) anal calc for C60H70Mg2N4 C 8044 Η 788 Ν 625 found C
8032 Η 806 Ν 639
S 6
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S3 1H NMR spectrum (400 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
S 5
Figure S4 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
Synthesis of [(MesNacnac)Mg2(-TS)] (7) [(MesNacnac)Mg2] (300 mg 0419 mmol) and trans-
stilbene (84 mg 0466 mmol) were dissolved in toluene (15mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred overnight after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of 7 (216 mg 57 ) NMR spectra of analytically
pure crystalline samples showed one other significant product in addition to 7 This is thought to be
a diastereomer which co-crystallises with 7 and cannot be separated The NMR assignments below
are only tentative Mp 130-133degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 148 (s 12H
NCCH3) 164 (broad 12H ArCH3) 208-216 (2 broad overlapping signals 24H ArCH3) 250 (s
2H MgC(Ph)H) 472 (s 2H NCCH) 649-734 (m 18H ArH) 13C1H NMR (75 MHz 298 K
C6D6) δ = 189 (ArCH3) 210 (ArCH3) 230 (NCCH3) 460 (MgCH(Ph) 950 (NCCH) 1163
1270 1289 1291 1293 1315 1331 1570 (ArC) 1682 (NCCH3) IR νcm-1 (ATR) 1654 (w)
1597 (m) 1541 (m) 1508(m) 1474 (m) 1446 (m) 1366 (s) 1313 (w) 1256 (m) 1197 (m) 1161
(m) 1106 (w) 1052 (m) 848 (w) 793 (m) 763 (m) 741 (m) 697 (s) EIMS (70eV) mz () 3573
(MesNacnacMg+ 100) anal calc for C60H70Mg2N4 C 8044 Η 788 Ν 625 found C
8032 Η 806 Ν 639
S 6
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S4 13C1H NMR spectrum (100 MHz C6D6) of an equilibrium mixture of 6
[(DepNacnac)Mg2] and -methyl styrene at 298 K
Synthesis of [(MesNacnac)Mg2(-TS)] (7) [(MesNacnac)Mg2] (300 mg 0419 mmol) and trans-
stilbene (84 mg 0466 mmol) were dissolved in toluene (15mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred overnight after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of 7 (216 mg 57 ) NMR spectra of analytically
pure crystalline samples showed one other significant product in addition to 7 This is thought to be
a diastereomer which co-crystallises with 7 and cannot be separated The NMR assignments below
are only tentative Mp 130-133degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 148 (s 12H
NCCH3) 164 (broad 12H ArCH3) 208-216 (2 broad overlapping signals 24H ArCH3) 250 (s
2H MgC(Ph)H) 472 (s 2H NCCH) 649-734 (m 18H ArH) 13C1H NMR (75 MHz 298 K
C6D6) δ = 189 (ArCH3) 210 (ArCH3) 230 (NCCH3) 460 (MgCH(Ph) 950 (NCCH) 1163
1270 1289 1291 1293 1315 1331 1570 (ArC) 1682 (NCCH3) IR νcm-1 (ATR) 1654 (w)
1597 (m) 1541 (m) 1508(m) 1474 (m) 1446 (m) 1366 (s) 1313 (w) 1256 (m) 1197 (m) 1161
(m) 1106 (w) 1052 (m) 848 (w) 793 (m) 763 (m) 741 (m) 697 (s) EIMS (70eV) mz () 3573
(MesNacnacMg+ 100) anal calc for C60H70Mg2N4 C 8044 Η 788 Ν 625 found C
8032 Η 806 Ν 639
S 6
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
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6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S5 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 7
Figure S6 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 7
S 7
Mg
N
N
Mes
Mes
Mg N
N
Mes
Mes
PhH
PhH
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
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6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Synthesis of [(DepNacnac)Mg2(-TS)] (8) [(DepNacnac)Mg2] (100 mg 0130 mmol) and trans-
stilbene (25 mg 0139 mmol) were dissolved in toluene (10mL) and stirred at room temperature
affording an orange solution after 1h The mixture was then stirred for 72h after which time
volatiles were removed in vacuo and the residue extracted with pentane (ca 5mL) The extract was
stored at -30 degC overnight yielding red crystals of red crystals of 8 (60 mg 49 ) NMR spectra of
analytically pure crystalline samples showed one other significant product in addition to 8 This is
thought to be a diastereomer which co-crystallises with 8 and cannot be separated The NMR
assignments below are only tentative Mp 186-189 degC 1H NMR (400 MHz 298K C6D6) δ =
100-123 (m of overlapping signals ArCH2CH3) 148 (s 12H NCCH3) 204-266 (m of
overlapping signals ArCH2CH3) 239 (s 2H MgC(Ph)H) 471 (s 2H NCCH) 638-727 (m 22H
ArH) 13C1H NMR spectra could not be assigned confidently due to two sets of signals observed
IR νcm-1 (ATR) 1619 (w) 1544 (s) 1516 (m) 1443 (m) 1395 (m) 1329 (m) 1263 (m) 1176 (m)
1104 (m) 1063 (w) 1020 (m) 929 (w) 861 (w) 795 (m) 760 (s) 697 (s) EIMS (70eV) mz ()
1741 (MeCNDep+ 100) 3332 (DepNacnacH-CH2CH3+ 18) 3473 (DepNacnacH-CH3
+ 26) 3853
(DepNacnacMg+ 17) anal calc for C64H78Mg2N4 C 8075 Η 826 Ν 589 found C
8057 Η 840 Ν 604
Figure S7 1H NMR spectrum (400 MHz 298 K C6D6) of a compound mixture containing 8
S 8
Mg
N
N
Dep
Dep
Mg N
N
Dep
Dep
PhH
PhH
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
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6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
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7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S8 13C1H NMR spectrum (75 MHz 298 K C6D6) of a compound mixture containing 8
Synthesis of [(MesNacnac)Mg2(-DPA)] (9) [(MesNacnac)Mg2] (500 mg 0698 mmol) and
diphenylacetylene (131 mg 0735 mmol) were dissolved in toluene (15mL) and stirred at room
temperature for 6 hours during which time the reaction mixture became an orange solution This
was concentrated in vacuo (to ca 5mL) and stored at -30 degC to give orange block like crystals of 9
overnight (429 mg 69 yield) Crystals suitable for x-ray diffraction were grown from a saturated
hexane solution stored at -30degC overnight Mp 203-206 degC 1H NMR (400 MHz 298 K C6D6) δ =
149 (s 12H ArCH3) 189 (s 24H ArCH3) 229 (s 12H NCCH3) 472 (s 2H NCCH) 641-643
(m 4H ArH) 678 (s 8H Mes ArH) 691-694 (m 4H ArH) 702-705 (m 2H ArH) 13C1H
NMR (75 MHz 298 K C6D6) δ = 190 (ArCH3) 211 (ArCH3) 229 (NCCH3) 949 (NCCH)
1229 1236 1292 1304 1316 1328 1448 (ArC) 1602 (MgC(Ph)) 1681 (NCCH3) IR νcm-1
(ATR) 1584 (w) 1542 (m) 1521 (m) 1449 (m) 1389 (s) 1365 (s) 1260 (m) 1196 (m) 1196 (m)
1016 (w) 854 (w) 767 (m) 756 (m) 742 (m) 705 (s) EIMS (70eV) mz () 1191 (Mes+ 40)
1601 (MeCNMes+ 82) 3573 (MesNacnacMg+ 100) anal calc for C60H68Mg2N4 C 8062 Η
767 Ν 627 found C 8047 Η 778 Ν 617
S 9
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S9 1H NMR spectrum (400 MHz 298 K C6D6) of 9
Figure S10 13C1H NMR spectrum (75 MHz 298 K C6D6) of 9
S 10
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Synthesis of [(LZn)2(-DPE)] (10) To a stirred solution of [(MesNacnac)Mg2] (020 g 0278
mmol) in toluene (30 mL) was added neat 11-diphenylethylene (0054 mL 0306 mmol) via a
microsyringe and the reaction mixture was then cooled to -80 degC To this was added a solution of
[LZnBr] (0410 g 0556 mmol) in toluene (20 mL) whereupon the reaction mixture darkened
slightly After warming to room temperature the orange-red colour of the solution faded to pale
orange After stirring for a further 1 h volatiles were removed in vacuo The residue was extracted
into pentane (15 mL) and stored at -30 degC overnight yielding colourless crystals of 10 (021 g 51
) Mp= 202-206 degC 1H NMR (400 MHz 298 K C6D6) δ = 065 (s 2H CH2CPh2) 086-106
(m 42H CH(CH3)2) and CH(CH3)2) 181 (s 3H ArCH3) 185 (s 3H ArCH3) 620 (s 2H
CHPh2) 622 (s 2H CHPh2) 650-743 (m 54H ArH) 13C1H NMR (400 MHz 298 K C6D6) δ
= 143 (CH(CH3)2) 149 (CH(CH3)2) 156 (CH2CPh2) 193 (CH(CH3)2) 195 (CH(CH3)2) 210
(ArCH3) 211 (ArCH3) 513 (CHPh2) 526 (CHPh2) 555 (CH2CPh2) 1245 1265 1266 1266
1269 1272 1276 1285 1286 1288 1289 1292 1294 1295 1299 1301 1303 1305
1306 1314 1410 1449 1455 1460 1461 1465 1467 1469 (Ar-C) 29Si1H NMR (400
MHz 298 K C6D6) δ = -219 28 IR υcm-1 (Nujol) 1597 (m) 1491 (s) 1458 (s) 1377 (s) 1228
(m) 1210 (m) 1127 (m) 1075 (m) 1030 (m) 879 (s) 858 (m) 820 (m) 744 (s) 661 (s) MSEI
mz () 1574 (SiPri3+ 65) 1671 (Ph2CH+ 100) 5954 (L+ 15) anal calc for C98H108N2Si2Zn2
C 7843 H 725 N 187 found C 7822 H 731 N 194
Figure S11 1H NMR spectrum (400 MHz 298 K C6D6) of 10
S 11
Zn
Zn
PhPh
HH L
L
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S12 13C1H NMR spectrum (75 MHz 298 K C6D6) of 10
Synthesis of [(TBoLZn)2(-DPA)] (11) To a stirred solution of [TBoLZnBr(THF)] (150mg 0217
mmol) in toluene (20mL) at -78 degC was added [(MesNacnac)Mg2(-DPA)] (97 mg 0108 mmol)
dissolved in toluene (10mL) The reaction mixture was warmed to room temperature over the
course of an hour and stirred overnight during which time a colourless precipitate formed The
reaction solution was filtered and volatiles removed in vacuo The residue was taken up in hexane
(ca 20mL) and stored at -30degC overnight yielding colourless crystals of 11 (85mg 62 ) Mp
120-123 degC (decomp) 1H NMR (400 MHz 298 K C6D6) δ = 003 (s 18H Si(CH3)3) 112-114 (d 3JHH = 69 Hz 24H CH(CH3)2) 122-123 (d 3JHH = 69 Hz 24H CH(CH3)2) 333 (sept 3JHH =
69Hz 8H CH(CH3)2) 596 (s 4H NCH) 689-720 (m 22H ArH) 13C1H NMR (75 MHz 298
K C6D6) δ = 49 (Si(CH3)3) 237 (CH(CH3)2) 258 (CH(CH3)2) 287 (CH(CH3)2) 1180 (NCH)
1245 1271 1293 1397 1471 1518 (ArC) 1688 (ZnC(Ph)) 11B1H NMR (128 MHz 298 K
C6D6) δ = 234 29Si1H NMR (80 MHz 298 K C6D6) δ = -11 IR νcm-1 (ATR) 1599 (w) 1466
(m) 1388 (m) 1365 (s) 1228 (m) 1111 (w) 1074 (w) 880 (w) 830 (w) 799 (w) 756 (m) 698 (s)
EIMS (70eV) mz () 4754 (TBoLH+ 100) a reproducible microanalysis could not be obtained as
the compound presistently co-crystallised with a small amount (ca 3) of the pro-ligand TBoLH
S 12
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S13 1H NMR spectrum (400 MHz 298 K C6D6) of 11
Figure S14 13C1H NMR spectrum (75 MHz 298 K C6D6) of 11
S 13
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S15 11B1H NMR spectrum (128 MHz 298 K C6D6) of 11
Figure S16 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 11
S 14
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Synthesis of [(PhBoLCdI)2] K[PhBoL] (070 g 100 mmol) was dissolved in THF (30 mL) and the
solution was added to a suspension of CdI2 (403 mg 110 mmol) in THF (20 mL) at -80 degC The
reaction mixture was warmed to room temperature and stirred for 12 hrs affording a bright yellow
solution Volatiles were removed in vacuo and the residue was extracted with hexane (30 mL) The
bright yellow extract was filtered and the filtrate concentrated to ca 10 mL affording bright yellow
crystals of the title compound overnight (076 g 85 ) Mp 221-224 degC 1Η ΝΜR (400 ΜΗz 298
Κ C6D6) δ = 111 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 115 (d J = 68 Ηz 24Η CΗ(CΗ3)2) 349
(sept J = 68 Ηz 8Η CΗ(CΗ3)2) 596 (s 4Η NCH) 698-756 (m 42Η ΑrΗ) 13C1H NMR (75
MHz 298 K C6D6) δ = 236 (CH(CH3)2) 256 (CH(CH3)2) 287 (CH(CH3)2) 1181 (NCH) 1257
1287 1297 1300 1355 1358 1388 1394 1476 (ArC) 29Si1H NMR (80 MHz 298 K
C6D6) δ = -195 11B1H NMR (128 MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR νcm-1 (Nujol) 2921 (s) 2853 (s) 1738 (m) 1574 (w) 1456 (s)
1401 (m) 1375 (s) 1353 (s) 1227 (m) 1146 (w) 1103 (m) 1070 (m) 984 (m) 932 (w) 894 (m)
800 (m) 758 (m) 725 (m) 697 (s) MSEI mz () 9015 (PhBoLCdI+ 203) 6615 (PhBoLH+ 782)
5834 (PhBoLH+-Ph 100) 2591 (Ph3Si+ 935) anal calc for C88H102B2I2N6Si2Cd2 C 5871 Η
571 Ν 467 found C 5860 Η 573 Ν 452
Figure S17 1H NMR spectrum (400 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 15
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S18 13C1H NMR spectrum (75 MHz 298 K C6D6) of [(PhBoLCdI)2]
Figure S19 29Si1H NMR spectrum (80 MHz 298 K C6D6) of [(PhBoLCdI)2]
S 16
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S20 11B1H NMR spectrum (128 MHz 298 K C6D6) of [(PhBoLCdI)2]
Synthesis of [PhBoLCdCdPhBoL] (12) To a stirred solution of [(MesNacnac)Mg2] (0082 g 0114
mmol) in hexane (30 mL) was added neat 11-diphenylethylene (0022 mL 0125 mmol) via a
microsyringe and the reaction mixture cooled to -80 degC A solution of [(PhBoLCdI)2] (0206 g 0114
mmol) in hexane (20 mL) was then added whereupon the reaction mixture darkened slightly After
warming to room temperature the orange-red colour of the solution faded to pale yellow After
stirring for a further 1 h volatiles were removed in vacuo The residue was extracted into hexane
(15 mL) and stored at -30 degC overnight yielding yellow crystals of 12 (0081 g 46 ) Mp = 124-
128 degC (decomposition) 1H NMR (400 MHz 298 K C6D6) δ = 108 (d 3JHH = 68 Hz 24H
CH(CH3)2) 123 (d 3JHH = 68 Hz 24H CH(CH3)2) 354 (sept 3JHH = 68 Hz 8H CH(CH3)2)
612 (s 4H NCH) 687-748 (m 42H ArH) 13C1H NMR (75 MHz 298 K C6D6) δ = 230
(CH(CH3)2) 256 (CH(CH3)2) 286 (CH(CH3)2) 1184 (NCH) 1286 1299 1354 1358 1360
1394 1401 1475 (ArC) 29Si1H NMR (80 MHz 298 K C6D6) δ = -207 11B1H NMR (128
MHz 298 K C6D6) δ = 242 no signal was observed in the 113Cd1H NMR spectrum IR υcm-1
(Nujol) 1623 (m) 1551 (m) 1457 (m) 1440 (m) 1401 (s) 1354 (s) 1259 (s) 1188 (m) 1148 (m)
1101 (s) 1071 (m) 1019 (m) 984 (m) 801 (s) 759 (m) 737 (m) MSEI mz () 2591 (SiPh3+
72) 3862 (BN(Dip)CH2+ 11) 6615 (PhBoLH+ 100) 7745 ((HC(Dip)N)2B(Ph2Si)NCd+ 2) a
reproducible microanalysis could not be obtained as the compound presistently co-crystallised with
a small amount (ca 3) of the pro-ligand PhBoLH
S 17
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S21 1H NMR spectrum (400 MHz 298 K C6D6) of 12
Figure S22 13C1H NMR spectrum (75 MHz 298 K C6D6) of 12
S 18
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S23 11B1H NMR spectrum (128 MHz 298 K C6D6) of 12
Synthesis of [LdaggerMgMg Ldagger] To a stirred solution of [(MesNacnac)Mg2] (052g 072 mmol) in
toluene (40 mL) at room temperature was added neat 11-diphenylethylene (014 mL 079 mmol)
via a microsyringe The yellow solution became red-orange and then red upon addition The
solution was then cooled to -78degC and to it was added dropwise solution of [(LdaggerMgI)2] (050g 036
mmol) in toluene (40 mL) The reaction mixture was then slowly warmed to room temperature over
12 h whereupon volatiles were removed in vacuo The residue was extracted into hexane (ca 20
mL) filtered and the filtrate concentrated to ca 5 mL This was stored at -30 degC overnight to give
colorless crystals of the title compound (032 g 80) Spectroscopic data were identical to those
previously reported8
Synthesis of [GeH(-NC-L-H)Mg(MesNacnac)] (13) To a stirred solution of
[(MesNacnac)Mg2] (020g 028 mmol) in toluene (40 mL) at room temperature was added neat
11-diphenylethylene (006 mL 033 mmol) via a microsyringe The yellow solution became red-
orange and then red upon addition The solution was then cooled to -78 degC and to it was added a
solution of [LGeCl] (020g 028 mmol) in toluene (40 mL) The reaction mixture was warmed to
room temperature over 12 h whereupon volatiles were removed in vacuo The residue was
extracted into hexane (ca 20 mL) filtered and the filtrate concentrated to ca 5 mL This was
stored at -30 ordmC overnight to give colorless crystals of 13 (018 g 56 ) Mp 158-163 degC 1H NMR
S 19
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
(400 MHz 298 K C6D6) δ = 123 (br s 6H ArCH3) 130-134 (m 18H CH(CH3)2) 151 (s 6H
ArCH3) 162 (sept 3JHH= 75 Hz 3H CH(CH3)2) 215 (s 3H ArCH3) 219 (s 6H ArCH3) 229
(s 6H NCCH3) 495 (s 1H NCCH) 640 cent (m 2H ArH) 656 (s 2H CHPh2) 672-790 (m
23H ArH) GeH resonance obscured 13C1H NMR (100 MHz 298 K C6D6) δ = 142
(CH(CH3)2) 203 (ArCH3) 205 (ArCH3) 229 (ArCH3) 240 (NCCH3) 480 (CHPh2) 510
(CHPh2) 953 (NCCH) 1250 1258 1286 1293 1302 1314 1335 1338 1407 1420 1430
1454 14901492 1496 1514 (ArC) 1685 (NCCH) 29Si1HNMR (C6D6 296 K 80 MHz) δ =
105 IR υcm-1 (Nujol) 1942 (s Ge-H) 1509 (m) 1447 (s) 1255 (s) 1146 (s) 907 (s) 885 (s) 769
(m) 697 (s) EIMS (70eV) mz () 1671 (CHPh2+ 100) 3573 (MesNacnacMg+ 50) 6674 (L-
HGe+ 10) anal calc for C65H77GeMgN3Si C 7614 H 757 N 410 found C7594
H 753 N405
Figure S24 1H NMR spectrum (400 MHz 298 K C6D6) of 13
S 20
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S25 13C1H NMR spectrum (75 MHz 298 K C6D6) of 13
Figure S26 29Si1H NMR spectrum (80 MHz 298 K C6D6) of 13
S 21
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Vant Hoff analysis of variable temperature 1H NMR spectra of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)]
In an NMR tube equipped with a JYoung stopper a solution of [(XylNacnac)Mg(μ-
CH2CPh2)Mg(XylNacnac)] C (4000 mg 00606 mmol) in toluene-d8 (600 uL 01010M) was
subject to a variable temperature 1H NMR spectroscopic analysis The integrals for the signals of
free diphenylethylene CPh2CH2 A protons and NCCH protons of the ligands of both C and
[(XylNacnac)Mg2] B were used for the determination of the equilibrium constant of the reaction
between B and A to give C Temperatures between 20 ordmC (293 K) to 60 ordmC (343 K) at 10 K
increments were used for the vant Hoff analysis
N
N
Xyl
Xyl
MgN
N
Xyl
Xyl
Mg N
N
Xyl
Xyl
MgN
NXyl
Xyl
MgPhPh
PhPh
HH
C7D8
A B C
The equilibrium constant (Keq) was calculated according to Equation 1
Keq =[A][B][C]
A vant Hoff plot of ln(Keq) against 1T was constructed for the above reaction ΔS and ΔH were
calculated using the slope and intercept of the plot (Figure S27) according to Equation 2
119897119899(119870119890119902) =‒‒ Δ119867119877119879
+ Δ119878119877
The free energy ΔG of the reaction was calculated according to Equation 3
Δ119866 = Δ119867 ‒ 119879Δ119878
S 22
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Tables of integrals and concentrations used to produce the vant Hoff plot are shown below
Table S1 Integrations from VT-NMR studies
T (K) A (DPE) B (Mg Dimer) C (Product 5)293 1088 1077 7805303 1509 1560 693313 1949 2021 6028323 2407 2409 5183333 2841 2951 4206343 3553 3575 2871353 Decomposition seen in the 1H NMR spectrum
above this temperature
Table S2 Table of calculated concentrations (molar)
T (K) [A] [B] [C]
293 123E-02 122E-02 887E-02
303 180E-02 186E-02 830E-02
313 246E-02 256E-02 763E-02
323 320E-02 320E-02 690E-02
333 407E-02 423E-02 603E-02
343 559E-02 562E-02 451E-02
Table S3 Keq and 1T values used for vant Hoff plot
T (K) Keq ln Keq 1T
293 587E+02 637E+00 341E-03
303 145E+02 550E+00 329E-03
313 120E+01 479E+00 319E-03
323 671E+01 420E+00 309E-03
333 349E+01 355E+00 300E-03
343 143E+01 266E+00 291E-03
S 23
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S27 Vant Hoff plot of lnK against 1T
Table S4 Calculated ΔS and ΔH values
Slope
6651
ΔS (Jmol-1K-1) ΔS (kcalmol-1K-1) ΔH (Jmol-1) ΔH (kcalmol-1)
Intercept
-16405 -136349 -003258 -552964 -132162
Table S5 Calculation of free enthalpy ΔG for varying temperatures
T (K) ΔG (kcalmol-1)
293 -3670
303 -3344
313 -3018
323 -2693
333 -2367
343 -2041
Estimate of error The uncertainty in integration was estimated to be 5 The variable temperature
NMR apparatus has an uncertainty of 1ordm The uncertainty of the concentration of C in C7D8 is 3
The overall uncertainty of the data is 10
S 24
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
2 X-Ray Crystallography
Crystals of 5-13 [LdaggerMgMgLdagger] and [(PhBoLCdI)2] suitable for X-ray structural determination were
mounted in silicone oil Crystallographic measurements were made using either an Oxford Gemini
Ultra or a Bruker X8 diffractometer using a graphite monochromator with Mo K radiation ( =
071073 Aring) or Cu K radiation (154180 Aring) or the MX1 beamline of the Australian Synchrotron (
= 071090 Aring) The software package Blu-Ice10 was used for synchrotron data acquisition while the
program XDS11 was employed for synchrotron data reduction All structures were solved by direct
methods and refined on F2 by full matrix least squares (SHELX-1612) using all unique data
Hydrogen atoms are typically included in calculated positions (riding model) Crystal data details
of data collections and refinements for all structures can be found in their CIF files and are
summarized in Table S6
S 25
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Table S6 Crystal data for 5-13 [LdaggerMgMg Ldagger] and [(PhBoLCdI)2]5 6 7 8 9 10(pentane)
empirical formula C56H62Mg2N4 C59H76Mg2N4 C60H70Mg2N4 C64H78Mg2N4 C60H68Mg2N4 C103H120N2Si2Zn2
formula weight 83971 88985 89582 95192 89380 157292crystal system monoclinic monoclinic orthorhombic triclinic triclinic monoclinicspace group P21c Cc Pbca P-1 P-1 Cca (Aring) 187478(10) 199645(7) 153389(6) 86500(3) 13659(4) 148102(4)b (Aring) 127752(9) 112773(4) 140741(5) 122882(5) 14429(4) 188756(4)c (Aring) 204162(10) 229784(8) 237894(10) 135191(5) 15718(5) 315018(9)α (ordm) 90 90 90 108311(4) 67851(10) 90β (ordm) 100287(5) 93089(3) 90 90582(3) 79390(10) 98531(2)γ (ordm) 90 90 90 100254(3) 66344(10) 90V (Aring3) 48112(5) 51660(3) 51357(3) 133907 26261(13) 87551(4)Z 4 4 4 1 2 4T (K) 123(2) 123(2) 123(2) 123(2) 123(2) 123(2)ρcalcd (gcm3) 1159 1144 1159 1180 1130 1193μ (mmndash1) 0091 0088 0089 0089 0087 0623
F(000) 1800 1928 1928 514 960 3360reflns collected 28117 22426 75822 22800 16900 33281unique reflns 8948 8241 5097 5809 16900 13774Rint 00336 00989 01204 00777 00000 00481R1 [I gt 2σ(I)] 00399 00921 00712 00533 00916 00460wR2 (all data) 01018 02705 02100 01501 02650 00917largest peak and hole (eAringndash3)
0265 -0235 1171 -0601 1125 -0446 0424 -0418 0481 -0511 0633 -0370
CCDC no 1890177 1890171 1890170 1890169 1890173 1890179
S 26
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
11 12(hexane) 13(hexane)15 (LdaggerMg)2 (PhBoLCdI)2(hexane)empirical formula C72H100B2N6Si2Zn2 C93H114B2Cd2N6Si2 C74H98GeMgN3Si C76H80Mg2N2Si2 C94H116B2Cd2I2N6Si2
formula weight 125811 161850 115454 112622 188632crystal system triclinic orthorhombic triclinic monoclinic monoclinicspace group P-1 P21212 P-1 P21c C2ca (Aring) 109999(4) 14733(3) 110530(7) 1110040(10) 234536(17)b (Aring) 124537(5) 27815(6) 129063(9) 162687(3) 110309(7)c (Aring) 132073(5) 11021(2) 234106(16) 183324(2) 33833(2)α (ordm) 92950(2) 90 99680(6) 90 90β (ordm) 90257(2) 90 97495(6) 1031710(10) 92003(3)γ (ordm) 1080410(10) 90 95233(5) 90 90V (Aring3) 171763(11) 45164(16) 32420(4) 322354(8) 87477(10)Z 1 2 2 2 4T (K) 123(2) 100(2) 123(2) 123(2) 150(2)ρcalcd (gcm3) 1216 1190 1183 1160 1432μ (mmndash1) 0778 0543 0544 1017 1268
F(000) 672 1696 1242 1204 3848reflns collected 22529 29143 37790 33951 64001unique reflns 6842 7903 12072 6726 6098Rint 00396 00337 00827 00593 001006R1 [I gt 2σ(I)] 00365 00424 00748 00451 00676wR2 (all data) 00825 01119 01982 01199 01299largest peak and hole (eAringndash3)
0417 -0403 0969 -1271 1631 -0883 0278 -0357 0693 -0953
CCDC no 1890174 1890172 1890176 1890178 1890175
S 27
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S28 ORTEP diagram of compound 7 (25 thermal ellipsoids hydrogen atoms except
alkenenic protons omitted) See Table 1 in main text for metrical parameters
Figure S29 ORTEP diagram of compound [LdaggerMgMgLdagger] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) Mg(1)-N(1) 19876(15) Mg(1)-Mg(1)
28085(11) N(1)-Mg(1)-Mg(1) 14948(5)
S 28
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
Figure S30 ORTEP diagram of compound [(PhBoLCdI)2] (25 thermal ellipsoids hydrogen atoms
omitted) Selected bond lengths (Aring) and angles (ordm) I(1)-Cd(1) 27077(8) I(1)-Cd(1) 29451(9)
Cd(1)-N(3) 2104(6) N(3)-Cd(1)-I(1) 15548(19) N(3)-Cd(1)-I(1) 11103(17) I(1)-Cd(1)-I(1)
9252(2)
3 References
1 S J Bonyhady D Collis N Holzmann A J Edwards R O Piltz G Frenking A Stasch
C Jones Nat Commun 2018 9 3079
2 S J Bonyhady C Jones S Nembenna A Stasch A J Edwards G J McIntyre Chem
Eur J 2010 16 938
3 R Lalrempuia C E Kefalidis S J Bonhady B Schwarze L Maron A Stasch C Jones
J Am Chem Soc 2015 137 8944
4 A J Boutland A Carroll C A Lamsfus A Stasch L Maron C Jones J Am Chem
Soc 2017 139 18190
5 J Hicks E J Underhill C E Kefalidis L Maron C Jones Angew Chem Int Ed 2015
54 10000
6 M J C Dawkins E Middleton C E Kefalidis D Dange M M Juckel L Maron C
Jones Chem Commun 2016 52 10490
7 J A Kelly M Juckel T J Hadlington I Fernandez G Frenking C Jones Chem Eur J
in press online article DOI 101002chem201804770
8 A J Boutland D Dange A Stasch L Maron C Jones Angew Chem Int Ed 2016 55
9239
9 T J Hadlington M Hermann J Li G Frenking C Jones Angew Chem Int Ed 2013
52 10389
10 TM McPhillips S McPhillips HJ Chiu AE Cohen AM Deacon PJ Ellis E Garman
A Gonzalez NK Sauter RP Phizackerley SM Soltis P Kuhn J Synchrotron Rad
2002 9 401
S 29
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30
11 WJ Kabsch Appl Cryst 1993 26 795
12 GM Sheldrick SHELX-16 University of Goumlttingen 2016
S 30