Supporting information for the manuscriptSupporting information for the manuscript Facile...
Transcript of Supporting information for the manuscriptSupporting information for the manuscript Facile...
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Supporting information for the manuscript
Facile N-functionalization and strong magnetic communication in a diuranium(V) bis-nitride complex
Luciano Barluzzia, Lucile Chatelaina, Farzaneh Fadaei-Tirania, Ivica Zivkovicb and Marinella
Mazzanti*a
aInstitut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland. bLaboratory for Quantum Magnetism, Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2019
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Contents
A) NMR SPECTRA .......................................................................................................................... 3
B) IR SPECTRA ............................................................................................................................. 26
C) X-RAY CRYSTALLOGRAPHIC DATA .......................................................................................... 28
D) MAGNETIC DATA .................................................................................................................... 30
E) UV-VIS DATA .......................................................................................................................... 35
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A) NMR spectra
Fig. S1: 1H-NMR (400 MHz) at 298 K in d8-thf of the crude reaction mixture between [U(OSi(OtBu)3)3]2, 1 and one equivalent of KN3 in thf after 4 days at -40°C leading to a mixture of complex [K{[U(OSi(OtBu)3)3]2(μ-N)}], 2 and complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3
Fig. S2: 1H-NMR (400 MHz) at 298 K in d8-thf of isolated [K{[U(OSi(OtBu)3)3]2(μ-N)}], 2
-8-7-6-5-4-3-2-1012345678f1(ppm)
-1.58
-0.68
1.73
2.60
3.58
thf[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3[K{[U(OSi(OtBu)3)3]2(μ-N)}], 2[U(OSi(OtBu)3)3]2, 1
-2.2-2.0-1.8-1.6-1.4-1.2-1.0-0.8-0.6-0.4-0.20.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.2f1(ppm)
-0.67
1.73
3.58
thf[K{[U(OSi(OtBu)3)3]2(μ-N)}], 2
-
Fig. S3: 1H-NMR (400 MHz) at 298 K in d8-thf of the reaction mixture between [U(OSi(OtBu)3)3]2, 1 and two equivalents of
KN3 in thf at -40°C for 5 days forming complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3
Fig. S4: 1H-NMR (400 MHz) at 298 K in d8-thf of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3
-5.5-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.0f1(ppm)
-1.58
thf[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3
-5.5-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
-1.58
thf[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3
-
Fig. S5: 13C-NMR (400 MHz) at 298 K in d8-thf of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3
Fig. S6: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3 at room
temperature
-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4[U(OSi(OtBu)3)4][K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3
immediately
7h
24h
3d
5d
-
Fig. S7: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3 after 24h at 70°C affording
complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
Fig. S8: 1H-NMR (400 MHz) at 298 K in d8-tol of [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3, after 5 days at RT (top) and after
24h at 70°C (bottom).
-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
-1.76
tol
[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4[U(OSi(OtBu)3)4][K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3
after 5d at RT
after 24h at 70°C
-
Fig. S9: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
Fig. S10: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
-1.76
-1.14
-0.86
1.40
1.63
2.09
7.02
7.10
tol
[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
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Fig. S11: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture 6h after the addition of one equivalent of CS2 to
[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5
Fig. S12: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5
-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
0.39
0.60
0.720.98
1.06
2.08
6.97
7.01
7.12
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
0.39
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5
-
Fig. S13: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}], 13C-5
Fig. S14: 13C-NMR (400MHz) at 298 K in d6-dmso of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}], 13C-5
-
Fig. S15: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-
N)2}], 4 and 10 equivalents of 13CS2 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}], 13C-5 and an unidentified precipitate
Fig. S16: 13C-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 10
equivalents of 13CS2
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
toluene[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5
immediately
24h
2030405060708090100110120130140150160170180190f1(ppm)
toluenesiloxide (C(CH3)3)
siloxide (C(CH3)3)NCS in complex 5unknown
CS2
-
Fig. S17: Quantitative 13C-NMR (600 MHz) at 298 K in d6-dmso of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 10 equivalents of 13CS2
Fig. S18: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of one equivalent of
CO2 to [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6
2030405060708090100110120130140150160170180f1(ppm)
1.38
1.00
d6-dmso
KNCS
toluene
CH313COONa
-
Fig. S19: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6
Fig. S20: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-N13CO)}], 13C-6
-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
0.18
2.08
6.97
7.01
7.09
toluene[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6
-
Fig. S21: 13C-NMR (400 MHz) at 298 K in D2O using d6-dmso as a reference of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-N13CO)}], 13C-6
Fig. S22: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 2 equivalents of CO2 to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
0.19
1.06
toluene[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6[U(OSi(OtBu)3)4]
-
Fig. S23: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 10 equivalents of
13CO2 to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
Fig. S24: 13C-NMR (400 MHz) at 298 K in d6-dmso of the reaction mixture after the addition of 10 eqvs of 13CO2 to complex
[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
-9-8-7-6-5-4-3-2-1012345678910f1(ppm)
0.45
0.741.06
1.56
2.08
6.97
7.09
toluene
-
Fig. S25: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 1 eqv of CO to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
Fig. S26: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 3 eqvs of CO to
complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7
-6-5-4-3-2-10123456789f1(ppm)
-1.76
0.78
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
0.78
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7
-
Fig. S27: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 1 atm of CO to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7
Fig. S28: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 6 atm of CO to
complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
-6-5-4-3-2-10123456789f1(ppm)
0.78
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
0.12
0.98
1.00
0.42
-0.52
0.26
0.78
1.06
1.34
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7[U(OSi(OtBu)3)4]
-
Fig. S29: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7
Fig. S30: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(µ-13CN)(μ-O)(µ-N13CO)}], 13C-7
-7-6-5-4-3-2-101234567891011f1(ppm)
-0.64
0.77
2.08
3.10
6.80
6.97
7.01
7.09
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7
-160-140-120-100-80-60-40-20020406080100120140160180200220f1(ppm)
-158.48
30.72
73.12
214.19
toluenesiloxide (C(CH3)3)
siloxide (C(CH3)3)
CN
NCO
oror
-
Fig. S31: Quantitative 13C-NMR (600 MHz) at 298 K in d6-dmso of isolated [K2{[U(OSi(OtBu)3)3]2(µ-13CN)(μ-O)(µ-N13CO)}],
13C-7
Fig. S32: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 1 atm
of H2 heated up at 60°C for 1h affording complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
3035404550556065707580859095100105110115120125130135140145150155160165170175f1(ppm)
0.96
1.00
d6-dmsoKNCOKCN
-
Fig. S33: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 1 atm of H2 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
Fig. S34: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 1 atm of H2 after 16h at RT affording complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
toluene[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
2.41
1.00
-1.77
-0.86
-0.23
2.08
6.97
7.01
7.09
0.68
1.00
-1.78
-0.87
-0.23
2.08
6.97
7.01
7.09
-0.87
-0.22
2.086.97
7.017.09
[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
1.00 2.41
1.00 0.68
immediately
8h
16h
-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
-0.87
-0.22
2.08
6.97
7.01
7.09
toluene[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
-
Fig. S35: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
Fig. S36: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8 on a broader spectral window
-11-10-9-8-7-6-5-4-3-2-10123456789101112f1(ppm)
-0.87
0.26
2.08
6.97
7.077.09
toluene[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
-30-20-100102030405060708090100110120130140150160170180190200f1(ppm)
162.00
1.69
-0.88
2.08
6.95
7.07
176.46
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
-
Fig. S37: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and D2 heated up at 60°C for 1h affording complex [K2{[U(OSi(OtBu)3)3]2(μ-ND)2}], 8
Fig. S38: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
-100102030405060708090100110120130140150160170180f1(ppm)
-0.85
2.08
6.97
7.01
7.09
toluene
[K2{[U(OSi(OtBu)3)3]2(μ-ND)2}], 8
-
Fig. S39: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 5.5
atm of H2 after 3h at RT
Fig. S40: 1H-NMR (400 MHz) at 298 K in d6-dmso of the volatiles and the headspace of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 5.5 atm of H2 after 3h at RT collected in a frozen 2M solution of HCl in Et2O
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
0.80
1.01
1.171.201.241.32
1.35
1.571.62
1.65
2.04
2.08
2.11
toluene
-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1(ppm)
1.04
3.42
4.22
Et2O
dmso
-
Fig. S41: 1H-NMR (400 MHz) at 298 K in d6-dmso of the reaction mixture between solid complex 4 and an excess of a 2M
solution of HCl in Et2O
Fig. S42: 1H-NMR (400 MHz) at 298 K in d6-dmso of the reaction mixture between solid complex 8 and an excess of a 2M
solution of HCl in Et2O
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1(ppm)
23.07
6.24
2.99
7.33
NH4Cldimethylsulfonedmso
-5-4-3-2-1012345678910f1(ppm)
89.00
5.64
NH4Cldimethylsulfonedmso
-
Fig. S43: 1H-NMR (400 MHz) at 298 K in d6-dmso of the reaction mixture between solid complex 8 and an excess of a 2M
solution of HCl in Et2O in presence of excess KC8
Fig. S44: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-
N)2}], 4 and 1 eq of PyHOTf
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1(ppm)
16.93
4.00
3.00
7.187.26
NH4Cldimethylsulfonedmso
-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
immediately
24h
3d
4d
5d
6d
7d
10d
-
Fig. S45: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8 and 1 eq of PyHOTf
Fig. S46: 1H-NMR (400 MHz) at 298 K in d6-dmso of the volatiles and the headspace of the reaction mixture between between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 30 eq of H2O in thf collected in a frozen 2M solution of HCl in Et2O
-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1(ppm)
tol
[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
immediately
12h
24h
36h
48h
60h
72h
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
12.10
0.19
7.03
7.167.29
NH4Cldimethylsulfonedmso
-
Fig. S47: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-
N)2}], 4 and 1 eq of Si2Me6. The formation of an unidentified yellow precipitate is also observed.
B) IR spectra
Fig. S48: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-S)(µ-N)(μ-NCS)}], 5 in a Nujol suspension measured on
KBr windows.
-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4Si2Me6
immediately
30 min
1h
2h
6h
12h
18h
1977
-
Fig. S49: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-N13CS)}], 5 in a Nujol suspension measured on KBr windows.
Fig. S50: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-NCO)}], 6 in a Nujol suspension measured on
KBr windows.
0
10
20
30
40
50
60
70
80
050010001500200025003000350040004500
%T
Wavenumber(cm-1 )
IRspectrumofcomplex[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}]
1931
-
Fig. S51: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-N13CO)}], 13C-6 in a Nujol suspension measured on KBr windows.
C) X-Ray crystallographic data 2 3 5
Formula C72H162KNO24Si6U2 C72H162K2N4O24Si6U2 C73H162K2N2O24S2Si6U2Crystal size (mm3) 0.642x0.503x0.419 0.48×0.31×0.26 0.12×0.06×0.04
crystal system Monoclinic Monoclinic monoclinicspace group P21/c P21/n P21volume (Å3) 10803(2) 5538.4(16) 5619.3(4)
a (Å) 14.210(3) 14.382(2) 13.9065(4)b (Å) 28.1537(19) 17.661(3) 18.2338(7)c (Å) 27.910(3) 21.819(4) 22.1810(9)α (deg) 90 90 90β (deg) 104.632(8) 92.012(9) 92.450(4)γ (deg) 90 90 90
Z 4 2 2 formula weight
(g/mol) 2109.72 2190.85 2238.96
density (g cm-3) 1.297 1.314 1.323absorption
coefficient (mm-1) 3.156 3.118 10.139
F(000) 4320 2240 2288 temp (K) 100(2) 100(2) 139.99(10)
total no. reflections 115428 97679 38004unique reflections
[R(int)] 24309[0.1089] 19106 [0.0447] 13621[0.0881]
-
Final R indices [I > 2σ(I)]
R1=0.0686,wR2=0.1330
R1 = 0.0592, wR2 = 0.1241
R1 = 0.0772, wR2 = 0.1898
Largest diff. peak and hole (e.A-3) 2.689and-2.107 4.561and -2.717 3.583and-4.163
GOOF 1.111 1.135 1.074
6 7 8 Formula C73H162K2N2O26Si6U2 C81H170K2N2O26Si6U2 C79H172K2N2O24Si6U2
Crystal size (mm3) 0.10×0.06×0.04 0.19×0.09×0.08 0.76×0.42×0.35cryst syst Monoclinic Monoclinic Monoclinic
space group P21 P21 P21/nvolume (Å3) 5510.8(3) 5673.2(9) 5536.5(3)
a (Å) 13.9377(5) 13.9927(15) 14.4207(4)b (Å) 17.9175(5) 18.2874(12) 17.5321(5)c (Å) 22.0849(6) 22.208(2) 21.9098(6)α (deg) 90 90 90 β (deg) 92.306(3) 93.321(7) 91.840(3)γ (deg) 90 90 90
Z 2 2 2formula weight
(g/mol) 2206.84 2310.98 2256.98
density (g cm-3) 1.330 1.353 1.354absorption
coefficient (mm-1) 10.000 3.049 3.121
F(000) 2256 2368 2316 temp (K) 100.00(10) 120(2) 140.01(10)
total no. reflections 39631 67143 73741unique reflections
[R(int)] 17996 [0.0796] 20671 [0.0523] 19069 [0.0618]
Final R indices [I > 2σ(I)]
R1 = 0.0640, wR2 = 0.1592
R1 = 0.0511, wR2 = 0.1029
R1 = 0.0390, wR2 = 0.0824
Largest diff. peak and hole (e.A-3) 2.543and -3.689 1.503and -0.802 2.543and -1.684
GOOF 1.017 1.067 1.060
-
D) Magnetic data
Fig. S52: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4
0 50 100 150 200 250 300Temperature (K)
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5-
0 (e
mu/
mol
Oe)
10-3
-
Fig. S53: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-S)(µ-N)(μ-NCS)}], 5
Fig. S54: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-NCO)}], 6
0 50 100 150 200 250 300Temperature (K)
1
1.5
2
2.5
3
3.5
-0
(em
u/m
ol O
e)
10-3
0 50 100 150 200 250 300Temperature (K)
6
7
8
9
10
11
12
13
-0
(em
u/m
ol O
e)
10-4
-
Fig. S55: c vs T plot for complex [K{[U(OSi(OtBu)3)3]2(μ-N)}], 2
0 50 100 150 200 250 300Temperature (K)
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
0.055
-0
(em
u/m
ol O
e)
-
Fig. S56: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3
Fig. S57: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7
0 50 100 150 200 250 300Temperature (K)
0.005
0.01
0.015
0.02
0.025
0.03
0.035
-0
(em
u/m
ol O
e)
0 50 100 150 200 250 300Temperature (K)
5.8
6
6.2
6.4
6.6
6.8
7
7.2
-0
(em
u/m
ol O
e)
10-3
-
Fig. S58: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
0 50 100 150 200 250 300Temperature (K)
0.005
0.01
0.015
0.02
0.025
0.03
-0
(em
u/m
ol O
e)
-
Fig. S59: Ortep diagram of the core showing the metrical parameters for the bridging atoms in complexes a) [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3; b) [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7; c) [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8
E) UV-Vis data
Fig. S60: UV-Vis absorption spectra in toluene solution of complexes 3-8.
U1 U1
N1
N2
N3
N4
3.6330(6) Å
124.6(7)°
91.5(4)°
U1 U1
N1
H1
3.5687(2) Å
106.10(12)°
U1 U2O2A
N1
C1A
O1A
90.7(6)°
N2
115.8(6)°
92.5(7)°
C2A
3.6358(7)Å
a) b)
c)
0
2000
4000
6000
8000
10000
250 750 1250 1750
ε(M
-1cm
-1)
wavelenght (nm)
345678
-
Fig. S61: NIR absorption spectra in toluene solution of complexes 3-8.
0
20
40
60
80
100
120
450 950 1450 1950
ε(M
-1cm
-1)
wavelenght (nm)
345678