Supporting Information� Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014

m-Metallaphenol: Synthesis and Reactivity Studies

Feifei Han, Tongdao Wang, Jinhua Li, Hong Zhang,* and Haiping Xia*[a]

chem_201304957_sm_miscellaneous_information.pdf

1

Supporting Information

A Novel m-Metallaphenol: Synthesis and Reactivity

Studies Feifei Han, Tongdao Wang, Jinhua Li, Hong Zhang,* and Haiping Xia*

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

E–mail: zh@xmu.edu.cn; hpxia@xmu.edu.cn

Contents

1. Crystallographic details

2. Cartesian coordinates for all of the calculated structures

2

1. Crystallographic details

Single-crystal X-ray diffraction data were collected on an Oxford Gemini S Ultra CCD Area Detector with

graphite-monochromated MoKa radiation (λ = 0.71073 Å). All of the Data were corrected for absorption effects using the

multi-scan technique. The structures were solved by direct methods, expanded by difference Fourier syntheses and refined

by full matrix least-squares on F2 using Bruker SHELXTL (Version 6.10) program package. Non-H atoms were refined

anisotropically unless otherwise stated. Hydrogen atoms were introduced at their geometric positions and refined as riding

atoms unless otherwise stated. The crystal suitable for X-ray diffraction was grown from the CHCl3 solution layered with

hexane for complex 7. The crystal suitable for X-ray diffraction was grown from the CH2Cl2 solution layered with hexane

for complex 8 and 12b. The solvent molecules CHCl3 in 7 are disordered and were refined with suitable restraints. The

solvent molecules CH2Cl2 in 8 are disordered and were refined with suitable restraints. CCDC-935259 (7), CCDC-964603

(8) and CCDC-974942 (12b), contain the supplementary crystallographic data for this paper. These data can be obtained

free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Table S1. Crystal data and structure refinement for 7, 8 and 12b.

7 8 12b

formula C67H56Cl6N3O2OsP3S2 C71H58Cl4N3O2OsP3S2 C63H52Cl5N2OOsP3S2

Mw 1495.08 1474.23 1377.55

T [K] 173(2) 173(2) 153(2)

λ [Å] (MoKα radiation) 0.71073 0.71073 0.71073

crystal system Monoclinic Triclinic Triclinic

space group P2(1)/c P-1 P-1

a [Å] 13.2243(2) 12.8223(4) 11.8909(5)

b [Å] 19.0975(4) 13.6512(10) 13.7815(5)

c [Å] 25.5554(4) 20.8025(10) 18.5424(8)

α [°] 90 78.109(5) 95.053(3)

3

β [°] 92.679(2) 73.630(4) 103.194(4)

γ [°] 90 69.890(5) 91.712(3)

V [Å3] 6446.99(19) 3256.5(3) 2943.0(2)

Z 4 2 2

ρcalcd [g cm-3] 1.540 1.503 1.555

μ [mm-1] 2.413 2.308 2.590

F(000) 3000 1484 1380

crystal size [mm3] 0.40×0.15×0.15 0.50×0.40×0.20 0.60×0.20×0.15

θ range [°] 2.62 to 26.37 3.05 to 25.00 3.18 to 25.00

total reflns 36945 23071 22539

unique reflns 13164 11450 10338

Observed reflns [I ≥ 2σ(I)] 10496 10780 9714

data/restraints/parameters 13164/60/794 11450/72/803 10338/0/694

GOF on F2 1.001 1.000 1.000

R1/wR2 [I ≥2σ(I)] 0.0414/0.0866 0.0283/0.0640 0.0341/0.0890

R1/wR2 (all data) 0.0590/0.0962 0.0309/0.0653 0.0368/0.0908

largest peak/hole [e Å-3] 0.929/-1.060 0.896/-0.869 1.837/-1.586

Table S2. Selected Bond Lengths and Angles for 12b.

12b

Bond Lengths (Å) Bond Angles (deg)

Os1—C1 1.970(4) C1—Os1—C5 88.90(17)

Os1—C5 1.942(4) Os1—C1—C2 130.8(3)

C1—C2 1.390(6) C1—C2—C3 123.4(4)

C2—C3 1.434(6) C2—C3—C4 121.1(4)

C3—C4 1.354(6) C3—C4—C5 128.2(4)

C4—C5 1.425(6) C4—C5—Os1 127.6(3)

4

C4—O1 1.410(5) C5—C4—O1 109.5(3)

C6—O1 1.358(5) C4—O1—C6 107.5(3)

C5—N1 1.388(5) O1—C6—N1 107.4(3)

C6—N1 1.357(5) C5—N1—C6 113.4(3)

C6—S1 1.646(4) C4—C5—N1 102.2(3)

2. Cartesian coordinates for all of the calculated structures

Os -1.222688 0.328197 0.124439 P -2.132445 -1.860685 -0.057421 P -0.637032 2.649709 0.060896 P 3.286626 -0.927787 0.091315 C 0.622601 -0.281980 -0.223105 H 0.798351 -0.566019 -1.091292 C 1.690288 -0.342662 0.658210 C 1.575580 -0.073684 2.027172 H 2.357833 -0.049668 2.530162 C 0.397928 0.154413 2.674282 C -0.863235 0.247962 2.025835 H -1.607442 0.274274 2.583269 C -2.805060 -2.627849 1.459454 C -2.754592 -4.014392 1.722428 H -2.242007 -4.570052 1.178558 C -3.463839 -4.550636 2.784979 H -3.407546 -5.460751 2.968728 C -4.247263 -3.750266 3.563151 H -4.732989 -4.123229 4.264662 C -4.329773 -2.383843 3.322772 H -4.871618 -1.842820 3.849563 C -3.581351 -1.836531 2.271720 H -3.611320 -0.918914 2.122540 C -3.617435 -2.064029 -1.115757 C -4.264319 -0.965276 -1.705600 H -3.913654 -0.110275 -1.605802 C -5.417946 -1.160428 -2.430630 H -5.848527 -0.427945 -2.809352 C -5.944372 -2.413889 -2.604861 H -6.706701 -2.532036 -3.125993 C -5.337642 -3.497064 -2.006491 H -5.708805 -4.345844 -2.089384 C -4.187708 -3.315337 -1.292492 H -3.774716 -4.055264 -0.910808 C -0.991140 -3.095310 -0.726008

C -0.024897 -3.671162 0.104682 H 0.030098 -3.414959 0.996507 C 0.843752 -4.613117 -0.395223 H 1.460675 -5.010984 0.175364 C 0.817074 -4.974020 -1.713419 H 1.392725 -5.627444 -2.037171 C -0.084827 -4.346041 -2.552853 H -0.082717 -4.554446 -3.459880 C -0.995704 -3.412088 -2.074407 H -1.599211 -3.005781 -2.652282 C 0.989115 3.088620 -0.594232 C 1.414635 2.448918 -1.759300 H 0.931513 1.728122 -2.093847 C 2.544879 2.879084 -2.413531 H 2.819931 2.440294 -3.188137 C 3.273897 3.938585 -1.949929 H 4.027162 4.228178 -2.412378 C 2.887780 4.569995 -0.801640 H 3.387701 5.281463 -0.474355 C 1.758090 4.151191 -0.126498 H 1.504906 4.587628 0.654355 C -0.757473 3.431674 1.698662 C -1.914124 4.019306 2.119689 H -2.624004 4.080723 1.524096 C -2.070097 4.522417 3.381760 H -2.877495 4.905326 3.636373 C -1.040359 4.455864 4.251903 H -1.130469 4.829523 5.097386 C 0.128510 3.852984 3.906340 H 0.820091 3.781081 4.523898 C 0.284660 3.339553 2.617511 H 1.085646 2.936628 2.372748 C -1.673562 3.739519 -0.986635 C -2.710601 3.280450 -1.751381 H -2.956488 2.386262 -1.695554 C -3.402169 4.120470 -2.606269 H -4.078952 3.779881 -3.144592 C -3.091885 5.448426 -2.656657 H -3.572044 6.008258 -3.224300 C -2.068587 5.979569 -1.876618 H -1.863489 6.886438 -1.898612 C -1.364076 5.097170 -1.065378 H -0.660862 5.426674 -0.553136

5

C 3.619130 -2.603864 0.693096 C 4.439411 -3.443298 -0.041684 H 4.810178 -3.163264 -0.847871 C 4.697828 -4.732153 0.462591 H 5.272131 -5.303644 0.005171 C 4.120791 -5.137356 1.599077 H 4.250660 -6.010707 1.887953 C 3.354197 -4.306269 2.334427 H 3.015644 -4.593775 3.151642 C 3.068251 -3.042139 1.890005 H 2.513478 -2.484303 2.385124 C 3.390445 -0.953986 -1.714503 C 4.292807 -0.120492 -2.367943 H 4.890787 0.404907 -1.888640 C 4.275621 -0.098248 -3.733029 H 4.884170 0.438843 -4.187184 C 3.379125 -0.847275 -4.445224 H 3.361385 -0.786759 -5.373602 C 2.527389 -1.675204 -3.812712 H 1.935771 -2.190118 -4.312926 C 2.515179 -1.772613 -2.422458 H 1.943347 -2.361630 -1.983525 C 4.586563 0.162047 0.682234 C 4.390828 1.521986 0.569769 H 3.566706 1.850613 0.290235 C 5.402567 2.386106 0.866083 H 5.255197 3.303372 0.820422 C 6.650074 1.903003 1.235912 H 7.347430 2.494655 1.409899 C 6.853150 0.535202 1.347511 H 7.683834 0.214945 1.619346 C 5.853350 -0.345519 1.065931 H 5.998738 -1.262579 1.122375 O 0.353123 0.319157 4.060514 H 1.110715 0.259565 4.368013 Cl -1.434962 0.285780 -2.115124 Cl -3.276358 1.125505 0.581865

PPh3

OH[Os]a

p-osmaphenol' Os -1.254534 0.328868 0.162932 P -2.160726 -1.861850 -0.014569 P -0.676726 2.652386 0.100885 P 3.257299 -0.913495 0.051588 C 0.586703 -0.274184 -0.217025 H 0.749316 -0.553665 -1.089242 C 1.668574 -0.335771 0.646755 C 1.575079 -0.073491 2.018626 C 0.407310 0.148087 2.685607 C -0.864369 0.240882 2.057920 H -1.599603 0.262388 2.627337 C -2.806667 -2.638048 1.509288 C -2.747952 -4.025640 1.764915 H -2.242552 -4.577238 1.210293 C -3.438486 -4.568922 2.836181 H -3.376604 -5.479707 3.014735 C -4.211639 -3.774511 3.630564

H -4.684952 -4.152173 4.338021 C -4.301970 -2.407239 3.397948 H -4.836858 -1.870285 3.935894 C -3.572114 -1.852826 2.337603 H -3.607142 -0.934620 2.193226 C -3.661919 -2.064709 -1.049890 C -4.321381 -0.965165 -1.624122 H -3.971647 -0.109594 -1.525955 C -5.485928 -1.160390 -2.331460 H -5.924663 -0.427445 -2.699788 C -6.011437 -2.414593 -2.503097 H -6.781689 -2.532593 -3.012482 C -5.392032 -3.498719 -1.919621 H -5.762008 -4.348208 -2.000527 C -4.231316 -3.316878 -1.223317 H -3.810099 -4.057333 -0.851780 C -1.026718 -3.089951 -0.707160 C -0.045592 -3.666767 0.105216 H 0.022969 -3.414542 0.997234 C 0.817654 -4.603796 -0.412971 H 1.444812 -5.002465 0.145775 C 0.770865 -4.958656 -1.732246 H 1.343141 -5.608851 -2.068250 C -0.146219 -4.329482 -2.554151 H -0.158066 -4.533668 -3.462062 C -1.052009 -3.400480 -2.056782 H -1.665896 -2.993298 -2.622990 C 0.937410 3.099180 -0.578179 C 1.346027 2.466163 -1.752910 H 0.859694 1.745490 -2.083038 C 2.464366 2.902730 -2.423164 H 2.728220 2.468362 -3.204131 C 3.197649 3.962237 -1.966354 H 3.942547 4.256219 -2.439465 C 2.828185 4.587157 -0.809072 H 3.331225 5.298587 -0.486518 C 1.710703 4.161858 -0.117866 H 1.468820 4.593910 0.668985 C -0.773130 3.426380 1.744020 C -1.924576 4.008599 2.186298 H -2.644103 4.070662 1.602464 C -2.061728 4.505381 3.453054 H -2.866044 4.884694 3.722378 C -1.017963 4.437862 4.306244 H -1.095573 4.807323 5.154806 C 0.146955 3.840080 3.939153 H 0.848568 3.767376 4.545193 C 0.283885 3.333104 2.645592 H 1.082005 2.933710 2.386125 C -1.733106 3.743949 -0.924763 C -2.780950 3.285343 -1.674918 H -3.023309 2.390176 -1.619346 C -3.488595 4.127255 -2.514654 H -4.172940 3.787150 -3.043643 C -3.183021 5.456350 -2.563788 H -3.673858 6.017375 -3.121025 C -2.148881 5.986917 -1.797784 H -1.946799 6.894486 -1.818814 C -1.428873 5.102868 -1.002095 H -0.718486 5.432087 -0.499661 C 3.604294 -2.591347 0.640094 C 4.415109 -3.424912 -0.111678

6

H 4.772069 -3.140036 -0.922387 C 4.685335 -4.715318 0.382340 H 5.253880 -5.282964 -0.086908 C 4.127800 -5.127509 1.526024 H 4.264829 -6.001800 1.808683 C 3.370698 -4.302133 2.277466 H 3.046147 -4.594437 3.098649 C 3.073979 -3.036813 1.843619 H 2.525608 -2.482937 2.350183 C 3.332187 -0.931004 -1.755767 C 4.221514 -0.091799 -2.419683 H 4.825583 0.433151 -1.947577 C 4.182349 -0.063272 -3.784199 H 4.781964 0.477733 -4.245534 C 3.276715 -0.811657 -4.485424 H 3.243897 -0.746887 -5.413105 C 2.437655 -1.645048 -3.843218 H 1.839582 -2.159398 -4.336285 C 2.448052 -1.748944 -2.453419 H 1.885056 -2.341694 -2.008136 C 4.563382 0.177457 0.626680 C 4.361913 1.537314 0.523746 H 3.532457 1.864775 0.259012 C 5.375762 2.403062 0.807839 H 5.225012 3.320087 0.768848 C 6.630446 1.921971 1.155340 H 7.328782 2.514887 1.320889 C 6.839263 0.554280 1.257253 H 7.675132 0.235243 1.514223 C 5.837636 -0.328104 0.987622 H 5.986578 -1.244978 1.037428 Cl -1.502614 0.296210 -2.073112 Cl -3.302905 1.117916 0.656976 H 0.389673 0.269263 3.748577 O 2.789629 -0.036579 2.772552 H 2.587728 -0.101729 3.708816

PPh3

[Os]a

o5-osmaphenol'HO

Os -1.193197 0.318808 0.116486 P -2.081405 -1.877024 -0.086858 P -0.625154 2.645058 0.068156 P 3.325870 -0.900796 0.172194 C 0.663573 -0.275932 -0.194780 H 0.859023 -0.557126 -1.059675 C 1.713788 -0.329463 0.707737 C 1.569423 -0.063657 2.074510 C 0.377200 0.153896 2.698144 C -0.871392 0.238355 2.024606 C -2.778149 -2.652057 1.415052 C -2.721777 -4.038577 1.676943 H -2.193894 -4.589204 1.142671 C -3.447879 -4.582249 2.724225 H -3.387941 -5.492181 2.907727 C -4.253223 -3.789483 3.487665 H -4.749920 -4.167490 4.178716 C -4.341921 -2.423376 3.247691

H -4.898595 -1.887594 3.764276 C -3.576973 -1.868340 2.212709 H -3.611350 -0.950752 2.064310 C -3.543135 -2.090578 -1.175141 C -4.186889 -0.996102 -1.776252 H -3.845218 -0.138472 -1.668162 C -5.324098 -1.199343 -2.524620 H -5.752885 -0.469730 -2.910844 C -5.836774 -2.456713 -2.711250 H -6.587498 -2.580137 -3.247780 C -5.233463 -3.535948 -2.102398 H -5.596016 -4.387550 -2.193989 C -4.099615 -3.346143 -1.365152 H -3.688413 -4.083346 -0.976332 C -0.916958 -3.101330 -0.734180 C 0.037016 -3.670747 0.114923 H 0.072006 -3.415569 1.008050 C 0.923117 -4.604861 -0.368802 H 1.531642 -4.998685 0.213488 C 0.925851 -4.963810 -1.687798 H 1.513151 -5.612050 -2.000872 C 0.035959 -4.341736 -2.544272 H 0.057980 -4.548632 -3.451379 C -0.891864 -3.415927 -2.082863 H -1.486899 -3.013544 -2.672157 C 1.010232 3.098111 -0.553491 C 1.464233 2.463761 -1.710709 H 0.993770 1.739650 -2.055965 C 2.603885 2.904078 -2.341445 H 2.897983 2.468784 -3.111009 C 3.314856 3.968650 -1.861715 H 4.074899 4.265052 -2.308496 C 2.900653 4.595053 -0.720493 H 3.388132 5.309984 -0.382173 C 1.761043 4.166069 -0.068823 H 1.488700 4.599175 0.707423 C -0.784797 3.423347 1.704320 C -1.954384 4.000963 2.102869 H -2.652625 4.057641 1.493213 C -2.139748 4.500737 3.362289 H -2.955166 4.876719 3.601179 C -1.127200 4.441047 4.252864 H -1.237299 4.812585 5.096914 C 0.053209 3.848158 3.929987 H 0.732797 3.780812 4.561220 C 0.239371 3.338111 2.643803 H 1.048342 2.942045 2.414603 C -1.649193 3.728205 -0.998399 C -2.666911 3.262059 -1.784520 H -2.906640 2.365831 -1.734967 C -3.347923 4.097884 -2.651902 H -4.010977 3.752741 -3.204227 C -3.047426 5.428375 -2.694083 H -3.520587 5.985253 -3.270440 C -2.044335 5.966457 -1.892841 H -1.846168 6.874982 -1.909370 C -1.349164 5.088429 -1.068900 H -0.659071 5.422742 -0.542136 C 3.659741 -2.575126 0.778069 C 4.501377 -3.406728 0.058695 H 4.885997 -3.122401 -0.739460 C 4.760011 -4.694286 0.566164

7

H 5.347988 -5.260388 0.119543 C 4.163543 -5.105978 1.690217 H 4.294631 -5.978728 1.980359 C 3.375638 -4.282291 2.411229 H 3.023063 -4.573849 3.221045 C 3.088479 -3.019777 1.963011 H 2.519380 -2.467234 2.447695 C 3.466167 -0.923203 -1.631207 C 4.374716 -0.081407 -2.265139 H 4.958680 0.448002 -1.773135 C 4.384788 -0.057068 -3.630261 H 4.997983 0.485645 -4.071294 C 3.508865 -0.812118 -4.361443 H 3.509298 -0.750228 -5.289901 C 2.651306 -1.647908 -3.747408 H 2.074038 -2.166746 -4.260176 C 2.611946 -1.747687 -2.357826 H 2.036186 -2.342004 -1.931350 C 4.604824 0.198494 0.790741 C 4.400409 1.556997 0.676368 H 3.579444 1.879439 0.380803 C 5.398975 2.428743 0.994241 H 5.245148 3.344868 0.946978 C 6.642661 1.955090 1.388368 H 7.331577 2.552049 1.577215 C 6.854495 0.588787 1.502011 H 7.682108 0.274780 1.790022 C 5.867702 -0.299489 1.199085 H 6.019330 -1.215441 1.257089 Cl -1.360072 0.278348 -2.126952 Cl -3.262019 1.098815 0.533698 H 0.320522 0.278086 3.759400 H 2.457064 -0.029744 2.671035 O -2.032746 0.268196 2.858432 H -1.766045 0.244173 3.780328

Os -1.234943 0.331033 0.195857 P -2.123926 -1.865504 0.003846 P -0.669055 2.657635 0.139783 P 3.285287 -0.885520 0.200790 C 0.618564 -0.262639 -0.136198 C 1.679021 -0.314965 0.754335 C 1.550044 -0.048493 2.122516 C 0.364851 0.168613 2.759561 C -0.891384 0.251861 2.100234 C -2.803006 -2.640164 1.514017 C -2.742722 -4.026499 1.776013 H -2.220584 -4.577072 1.236070 C -3.456489 -4.570072 2.831792 H -3.393852 -5.479860 3.015101 C -4.253625 -3.777418 3.603913 H -4.742168 -4.155371 4.300782 C -4.345969 -2.411504 3.364212 H -4.897089 -1.875806 3.886806 C -3.593227 -1.856536 2.320284

H -3.629910 -0.939054 2.171781 C -3.597806 -2.080643 -1.067609 C -4.249098 -0.986933 -1.661955 H -3.906798 -0.129014 -1.558234 C -5.394616 -1.191351 -2.397218 H -5.828263 -0.462241 -2.778937 C -5.908535 -2.449167 -2.577307 H -6.665234 -2.573392 -3.105188 C -5.297604 -3.527659 -1.974767 H -5.660602 -4.379554 -2.061756 C -4.155566 -3.336685 -1.250581 H -3.739467 -4.073396 -0.866061 C -0.966099 -3.089393 -0.656015 C -0.002137 -3.657699 0.182487 H 0.042845 -3.401999 1.075017 C 0.879029 -4.591491 -0.310779 H 1.494409 -4.984583 0.264763 C 0.866991 -4.951174 -1.629523 H 1.451127 -5.599197 -1.948905 C -0.033012 -4.330173 -2.476154 H -0.021179 -4.537561 -3.383339 C -0.956146 -3.404727 -2.004723 H -1.558122 -3.003070 -2.587427 C 0.958842 3.111433 -0.500690 C 1.400069 2.476741 -1.662652 H 0.926195 1.752123 -2.002131 C 2.532170 2.917467 -2.306562 H 2.817783 2.481940 -3.079185 C 3.247838 3.982781 -1.835543 H 4.002545 4.279441 -2.291110 C 2.846230 4.609544 -0.690026 H 3.337047 5.324990 -0.357670 C 1.714402 4.180163 -0.025189 H 1.450621 4.613521 0.753869 C -0.810588 3.436731 1.777229 C -1.975952 4.013788 2.188748 H -2.681126 4.069659 1.587048 C -2.147305 4.514141 3.449921 H -2.960204 4.889712 3.697871 C -1.124645 4.455625 4.328945 H -1.225379 4.827561 5.173989 C 0.052412 3.863345 3.992978 H 0.739187 3.796805 4.616471 C 0.224265 3.352704 2.705039 H 1.030841 2.957051 2.466863 C -1.705899 3.739502 -0.915642 C -2.732185 3.272237 -1.689870 H -2.970730 2.375877 -1.637098 C -3.423590 4.107123 -2.549904 H -4.092656 3.761229 -3.094456 C -3.124490 5.437790 -2.596235 H -3.604556 5.994031 -3.167476 C -2.112706 5.976990 -1.806761 H -1.915353 6.885638 -1.826045 C -1.407609 5.099887 -0.990304 H -0.711790 5.434955 -0.471614 C 3.627163 -2.559287 0.803747 C 4.461116 -3.390729 0.075297 H 4.836433 -3.106591 -0.727341 C 4.726377 -4.677830 0.580498 H 5.309614 -5.243789 0.127525 C 4.143021 -5.089293 1.711495

8

H 4.277992 -5.961793 2.000606 C 3.362819 -4.265730 2.440975 H 3.019683 -4.557071 3.254913 C 3.069725 -3.003659 1.995360 H 2.505808 -2.451225 2.486187 C 3.405061 -0.908840 -1.604079 C 4.305768 -0.066792 -2.248776 H 4.894937 0.463282 -1.763742 C 4.300283 -0.043208 -3.613937 H 4.908052 0.499668 -4.062221 C 3.416603 -0.799251 -4.334685 H 3.406426 -0.737879 -5.263121 C 2.566653 -1.635271 -3.710467 H 1.983936 -2.154781 -4.216345 C 2.543181 -1.734300 -2.320472 H 1.972713 -2.328763 -1.887142 C 4.570457 0.214970 0.804132 C 4.363838 1.573271 0.691345 H 3.539344 1.895000 0.404968 C 5.365370 2.445862 0.997350 H 5.210397 3.361857 0.951337 C 6.613780 1.973259 1.377556 H 7.304398 2.570784 1.558219 C 6.827816 0.607162 1.489532 H 7.658865 0.293869 1.768277 C 5.838238 -0.281942 1.198348 H 5.991134 -1.197759 1.255127 Cl -1.427317 0.289210 -2.045514 Cl -3.299407 1.109891 0.636162 H 0.320173 0.293357 3.821325 H 2.444395 -0.013653 2.708880 H -1.753225 0.273957 2.733985 O 0.904160 -0.695451 -1.468867 H 1.513538 -0.079475 -1.882185

Os 1.105237 0.092950 -0.181383 P 1.600612 -2.230367 -0.087918 P 0.947429 2.477349 -0.019560 P -3.556484 -0.324452 -0.262817 C -0.826730 -0.186579 0.114523 H -1.068877 -0.470675 0.966562 C -1.869292 -0.015049 -0.782134 C -1.679501 0.286613 -2.135848 H -2.433936 0.473495 -2.647119 C -0.466850 0.324599 -2.756879 C 0.776733 0.160164 -2.088873 H 1.524850 0.074714 -2.635030 C 2.154890 -3.041621 -1.629510 C 1.860229 -4.383549 -1.956015 H 1.244522 -4.859619 -1.444587 C 2.482819 -4.993888 -3.032803 H 2.266857 -5.870042 -3.258536 C 3.413920 -4.316563 -3.763678 H 3.838723 -4.741282 -4.475229

C 3.736923 -2.999253 -3.460252 H 4.378404 -2.543599 -3.954915 C 3.078049 -2.370446 -2.394944 H 3.270199 -1.480676 -2.203734 C 3.002149 -2.744526 0.978832 C 3.824508 -1.807436 1.626303 H 3.636224 -0.899552 1.561124 C 4.908602 -2.239265 2.356284 H 5.456476 -1.613819 2.773431 C 5.196188 -3.573680 2.479887 H 5.913650 -3.850202 3.004736 C 4.416305 -4.502386 1.825118 H 4.626219 -5.407158 1.873954 C 3.333188 -4.084886 1.105592 H 2.801326 -4.720711 0.685370 C 0.241419 -3.264764 0.509160 C -0.795511 -3.619937 -0.359117 H -0.784800 -3.320328 -1.238967 C -1.830222 -4.409077 0.086268 H -2.496898 -4.663807 -0.509648 C -1.896538 -4.824543 1.386880 H -2.587355 -5.375866 1.673180 C -0.913642 -4.406856 2.265450 H -0.972186 -4.649792 3.161937 C 0.160702 -3.634151 1.841672 H 0.815560 -3.369004 2.445082 C -0.585905 3.175708 0.634177 C -1.144071 2.574864 1.763384 H -0.806163 1.764827 2.070847 C -2.191331 3.174711 2.422127 H -2.557139 2.760567 3.172375 C -2.707167 4.367615 1.998064 H -3.405150 4.769120 2.463623 C -2.189594 4.966746 0.884740 H -2.545856 5.770358 0.583892 C -1.140392 4.379052 0.205620 H -0.796381 4.795117 -0.551253 C 1.241111 3.293404 -1.618328 C 2.493373 3.678827 -1.997411 H 3.190156 3.585074 -1.390668 C 2.763823 4.198493 -3.233161 H 3.632217 4.439058 -3.459783 C 1.757283 4.356895 -4.118444 H 1.930938 4.743612 -4.944808 C 0.491818 3.961915 -3.815591 H -0.188409 4.042981 -4.444519 C 0.218775 3.431006 -2.553585 H -0.646726 3.170030 -2.337633 C 2.141826 3.315511 1.089629 C 3.062773 2.643847 1.845773 H 3.144176 1.723086 1.752384 C 3.876831 3.307360 2.746769 H 4.469630 2.827078 3.277567 C 3.810581 4.666207 2.853675 H 4.372095 5.105001 3.452294 C 2.916485 5.406841 2.085714 H 2.878183 6.334100 2.146404 C 2.081138 4.702183 1.226220 H 1.459805 5.175260 0.720635 C -4.173756 -1.885278 -0.944529 C -5.147257 -2.592452 -0.259245 H -5.477978 -2.284339 0.554091

9

C -5.623746 -3.790422 -0.824972 H -6.301209 -4.267174 -0.401403 C -5.105953 -4.244887 -1.971319 H -5.385442 -5.067106 -2.301321 C -4.186741 -3.536151 -2.658235 H -3.888817 -3.845292 -3.483336 C -3.686407 -2.364922 -2.153072 H -3.029833 -1.896440 -2.615167 C -3.700772 -0.408134 1.538466 C -4.451069 0.546674 2.217693 H -4.934216 1.191726 1.755272 C -4.458474 0.507374 3.582483 H -4.969269 1.126144 4.052873 C -3.727019 -0.421443 4.271136 H -3.717905 -0.404675 5.201458 C -3.025934 -1.362489 3.612423 H -2.547582 -1.996974 4.096128 C -3.002680 -1.401300 2.219442 H -2.537687 -2.065073 1.761424 C -4.625599 1.007233 -0.819925 C -4.189776 2.303071 -0.643127 H -3.325826 2.464562 -0.338461 C -5.022388 3.348189 -0.912584 H -4.712710 4.220719 -0.823302 C -6.328699 3.115569 -1.319863 H -6.903930 3.830760 -1.475551 C -6.773179 1.813302 -1.496247 H -7.642230 1.660897 -1.792924 C -5.955000 0.754665 -1.242415 H -6.262468 -0.117563 -1.342434 S 0.864719 -0.880156 4.572091 S 5.671314 1.430768 -1.315796 C 1.075436 -0.366977 3.038646 C 4.203251 0.875444 -0.872714 N 1.251172 -0.072610 1.930925 N 3.156973 0.499202 -0.553866 O -0.364268 0.537267 -4.133482 H -1.113614 0.629220 -4.452977

Os 1.082728 0.025470 -0.204264 P 1.558391 -2.382248 -0.155076 P 1.228730 2.469607 -0.059222 P -3.619661 -0.143758 -0.165464 C -0.823248 -0.130186 0.146651 H -1.118255 -0.221638 1.196963 C -1.917862 -0.124886 -0.756221 C -1.723116 -0.015237 -2.169152 C -0.490846 0.070716 -2.795295 C 0.743085 0.102623 -2.108118 H 1.596020 0.205636 -2.793693 C 1.746657 -3.189406 -1.834089 C 1.134096 -4.394761 -2.204755 H 0.476280 -4.911844 -1.514753 C 1.369002 -4.952943 -3.465319 H 0.882631 -5.886862 -3.736482

C 2.228002 -4.321755 -4.364075 H 2.412842 -4.757807 -5.342606 C 2.857621 -3.130790 -3.993369 H 3.540268 -2.637415 -4.680494 C 2.621136 -2.565167 -2.740562 H 3.125376 -1.646123 -2.453185 C 3.110608 -3.000790 0.681044 C 3.897488 -2.173621 1.490502 H 3.614125 -1.141360 1.634840 C 5.038836 -2.687385 2.112516 H 5.642889 -2.033663 2.735998 C 5.405369 -4.020777 1.933914 H 6.296494 -4.413175 2.417718 C 4.623833 -4.850493 1.126030 H 4.901530 -5.890761 0.976244 C 3.485274 -4.343178 0.501681 H 2.893350 -4.996618 -0.131756 C 0.239748 -3.384266 0.700034 C -0.996257 -3.620628 0.076076 H -1.178673 -3.235212 -0.921958 C -1.991938 -4.357601 0.721031 H -2.933036 -4.548958 0.212427 C -1.779759 -4.839321 2.016208 H -2.552748 -5.415873 2.518129 C -0.570812 -4.571302 2.660180 H -0.399376 -4.929310 3.672025 C 0.434036 -3.853182 2.006807 H 1.369140 -3.654546 2.517256 C -0.189316 3.377800 0.764127 C -0.719030 2.813793 1.936339 H -0.347548 1.852743 2.284794 C -1.690258 3.498543 2.670627 H -2.082626 3.050836 3.579365 C -2.151368 4.746450 2.245573 H -2.905726 5.277740 2.820611 C -1.627106 5.314560 1.082834 H -1.966568 6.292881 0.750540 C -0.648660 4.637902 0.349306 H -0.242385 5.101532 -0.543400 C 1.354567 3.232870 -1.750790 C 2.615577 3.460748 -2.322645 H 3.512281 3.251678 -1.751151 C 2.722098 3.933722 -3.632135 H 3.706626 4.103991 -4.059562 C 1.576118 4.183733 -4.388567 H 1.662161 4.558606 -5.405237 C 0.317832 3.941212 -3.833812 H -0.581252 4.123930 -4.417397 C 0.207687 3.458914 -2.528733 H -0.776422 3.256189 -2.118655 C 2.644118 3.257830 0.868793 C 3.430828 2.516602 1.757431 H 3.244722 1.458390 1.882615 C 4.436523 3.150195 2.492007 H 5.040377 2.564800 3.180278 C 4.670120 4.517114 2.343901 H 5.457288 5.003054 2.915089 C 3.886050 5.261194 1.458974 H 4.058066 6.327572 1.336300 C 2.875771 4.635885 0.729336 H 2.272530 5.226735 0.046791 C -4.616052 -1.631066 -0.636391

10

C -5.781401 -1.928735 0.089099 H -6.088234 -1.293332 0.914488 C -6.543964 -3.051060 -0.235137 H -7.443201 -3.272675 0.332671 C -6.144918 -3.890777 -1.277417 H -6.735615 -4.768234 -1.525576 C -4.982140 -3.603897 -1.995234 H -4.664555 -4.256653 -2.803474 C -4.218075 -2.478806 -1.678666 H -3.320947 -2.259562 -2.243394 C -3.693999 -0.133956 1.670882 C -4.314837 0.911472 2.367008 H -4.728366 1.758889 1.832311 C -4.399215 0.865911 3.760916 H -4.884589 1.678317 4.294450 C -3.860006 -0.212693 4.462249 H -3.919123 -0.240456 5.546761 C -3.242258 -1.257189 3.769310 H -2.812278 -2.096947 4.306323 C -3.164533 -1.226625 2.378772 H -2.689487 -2.048097 1.853308 C -4.534133 1.344487 -0.753009 C -3.889717 2.586879 -0.645758 H -2.885649 2.651020 -0.236895 C -4.542195 3.746128 -1.065728 H -4.037835 4.702835 -0.969533 C -5.829611 3.672235 -1.603260 H -6.333278 4.576266 -1.934609 C -6.467756 2.435741 -1.717109 H -7.466635 2.373155 -2.139910 C -5.824905 1.271839 -1.291315 H -6.324966 0.314388 -1.391373 H -0.501251 0.138148 -3.887181 O -2.874587 -0.001969 -2.916486 H -2.636511 0.120393 -3.850574 N 1.276208 -0.126576 1.931607 N 3.164434 0.252617 -0.691503 C 1.382879 -0.210403 3.109178 C 4.312142 0.377850 -0.960132 S 5.905200 0.551677 -1.332999 S 1.530943 -0.326759 4.743686

PPh3

[Os]

o5-osmaphenolHO

Os 1.022808 0.053611 -0.173974 P 1.624970 -2.319853 -0.110082 P 1.020428 2.513999 -0.075105 P -3.667120 -0.266166 -0.183654 C -0.882912 -0.194330 0.157864 H -1.157976 -0.442153 1.188678 C -1.971563 -0.072579 -0.731611 C -1.791033 0.172249 -2.129686 C -0.574226 0.252874 -2.754158 C 0.709415 0.139024 -2.098737 C 2.002183 -3.090989 -1.772550 C 1.406392 -4.261457 -2.263414 H 0.649432 -4.778465 -1.684043

C 1.793019 -4.790406 -3.498669 H 1.322002 -5.700182 -3.863276 C 2.785419 -4.162886 -4.251310 H 3.089319 -4.577775 -5.209333 C 3.392523 -3.003839 -3.761330 H 4.173782 -2.512185 -4.335568 C 3.006723 -2.466728 -2.533061 H 3.477046 -1.562151 -2.159235 C 3.131323 -2.887839 0.841270 C 3.808333 -2.056682 1.741283 H 3.465914 -1.043804 1.896943 C 4.919780 -2.541212 2.437104 H 5.439264 -1.883734 3.129210 C 5.365123 -3.848329 2.244388 H 6.232881 -4.216963 2.786135 C 4.693165 -4.682049 1.347055 H 5.032853 -5.701929 1.184727 C 3.585740 -4.203986 0.648127 H 3.080153 -4.859241 -0.054556 C 0.287298 -3.404601 0.608107 C -0.910036 -3.613232 -0.096689 H -1.051475 -3.149306 -1.067989 C -1.918428 -4.421940 0.431981 H -2.825488 -4.594047 -0.141317 C -1.761906 -5.003819 1.693800 H -2.545125 -5.635724 2.105249 C -0.594873 -4.764912 2.420450 H -0.466392 -5.201374 3.407668 C 0.425066 -3.976945 1.880131 H 1.329751 -3.807512 2.452469 C -0.451743 3.369751 0.711000 C -1.020483 2.766620 1.844655 H -0.647306 1.804030 2.185694 C -2.027390 3.419332 2.560657 H -2.445418 2.942872 3.443163 C -2.487518 4.673340 2.154003 H -3.269942 5.179298 2.714307 C -1.922225 5.282724 1.031689 H -2.257369 6.268268 0.716852 C -0.905547 4.640217 0.320582 H -0.461685 5.141568 -0.532795 C 1.159333 3.239600 -1.783801 C 2.432281 3.328222 -2.371525 H 3.307146 3.025634 -1.806376 C 2.572391 3.764538 -3.689839 H 3.565081 3.828017 -4.127675 C 1.448877 4.109655 -4.444118 H 1.561726 4.455854 -5.468518 C 0.178392 3.999481 -3.876394 H -0.704597 4.254697 -4.457394 C 0.033616 3.559287 -2.558586 H -0.962617 3.460975 -2.140994 C 2.372139 3.404710 0.859677 C 3.053614 2.776308 1.908838 H 2.841997 1.740425 2.142859 C 3.993679 3.490598 2.655305 H 4.517515 2.991119 3.466108 C 4.267563 4.826706 2.362275 H 5.004948 5.375170 2.943364 C 3.589588 5.457196 1.316973 H 3.794973 6.497698 1.077837 C 2.644059 4.751653 0.572668

11

H 2.127672 5.255129 -0.238614 C -4.497901 -1.789705 -0.828448 C -5.617762 -2.319672 -0.168077 H -5.986066 -1.852780 0.740499 C -6.252189 -3.458115 -0.667047 H -7.115400 -3.864444 -0.147367 C -5.773758 -4.076124 -1.824947 H -6.266718 -4.964316 -2.210353 C -4.656604 -3.555574 -2.481853 H -4.275752 -4.037646 -3.377740 C -4.016977 -2.418045 -1.985663 H -3.138228 -2.030332 -2.490518 C -3.829838 -0.358291 1.639564 C -4.488255 0.647999 2.359454 H -4.905093 1.507661 1.846579 C -4.602619 0.547109 3.747572 H -5.116254 1.328035 4.301249 C -4.057201 -0.547950 4.419208 H -4.140392 -0.618567 5.500192 C -3.402653 -1.552660 3.702481 H -2.968573 -2.403750 4.218085 C -3.292034 -1.466547 2.315949 H -2.786309 -2.256409 1.770381 C -4.676751 1.156323 -0.779129 C -4.117526 2.441233 -0.678115 H -3.116987 2.571578 -0.277268 C -4.849811 3.552807 -1.095209 H -4.410801 4.541723 -1.004120 C -6.131993 3.390509 -1.625665 H -6.697303 4.257638 -1.956225 C -6.686144 2.113610 -1.735269 H -7.680602 1.983499 -2.152962 C -5.963989 0.996660 -1.311482 H -6.401241 0.008101 -1.404874 H -0.584469 0.419304 -3.835038 H -2.673817 0.297210 -2.756948 O 1.739022 0.138086 -2.979885 H 1.408180 0.190893 -3.896238 N 1.133615 -0.067585 1.969605 N 3.132302 0.390110 -0.416257 C 1.194723 -0.134422 3.151751 C 4.295651 0.575684 -0.549872 S 1.279344 -0.226977 4.788755 S 5.906624 0.832660 -0.734898

Os -1.087204 -0.035544 -0.219800 P -1.571585 2.366594 -0.113843 P -1.221636 -2.487109 -0.084419 P 3.660394 0.147909 -0.195545 C 0.826768 0.154711 0.203931 C 1.935902 0.000899 -0.706426 C 1.759313 -0.138705 -2.107185 C 0.543270 -0.156667 -2.771472 C -0.705738 -0.090733 -2.115177 C -1.555506 3.226509 -1.774656

C -0.826805 4.389233 -2.057874 H -0.204408 4.846033 -1.296384 C -0.904457 4.984033 -3.321580 H -0.331420 5.885524 -3.525110 C -1.719829 4.433102 -4.309163 H -1.782299 4.898613 -5.289580 C -2.464178 3.284428 -4.026552 H -3.113038 2.853926 -4.784863 C -2.384646 2.682592 -2.771432 H -2.975206 1.796638 -2.553141 C -3.228191 2.933243 0.540414 C -3.990133 2.134373 1.402454 H -3.634870 1.150362 1.674544 C -5.196379 2.614174 1.918590 H -5.777928 1.982227 2.584647 C -5.657663 3.885969 1.578628 H -6.600278 4.251555 1.978537 C -4.902711 4.686817 0.719449 H -5.251961 5.679201 0.445666 C -3.695729 4.214299 0.203822 H -3.123271 4.847758 -0.466103 C -0.393748 3.359907 0.938986 C 0.938566 3.531575 0.533018 H 1.273578 3.102142 -0.405020 C 1.840489 4.250801 1.318344 H 2.860723 4.393002 0.970831 C 1.430696 4.782462 2.543993 H 2.131037 5.341278 3.159802 C 0.117156 4.589861 2.972515 H -0.209744 4.989594 3.928856 C -0.790970 3.889127 2.174937 H -1.809236 3.752941 2.520339 C 0.334740 -3.359121 0.477983 C 0.915233 -2.895811 1.670555 H 0.483923 -2.037359 2.176099 C 2.024674 -3.542528 2.215097 H 2.457523 -3.173545 3.140510 C 2.575819 -4.657241 1.576529 H 3.437065 -5.163814 2.005149 C 2.006346 -5.123611 0.391092 H 2.417327 -5.999163 -0.106167 C 0.889410 -4.481180 -0.154671 H 0.445389 -4.869688 -1.064799 C -1.659501 -3.309167 -1.696951 C -2.941674 -3.833470 -1.908139 H -3.680200 -3.794066 -1.116155 C -3.282653 -4.395213 -3.140529 H -4.284247 -4.790120 -3.288514 C -2.348836 -4.445875 -4.175353 H -2.615523 -4.886591 -5.132548 C -1.070840 -3.918816 -3.976630 H -0.337654 -3.944968 -4.778987 C -0.730722 -3.346659 -2.750327 H 0.256729 -2.918144 -2.618616 C -2.451676 -3.252341 1.100010 C -3.550744 -2.530908 1.583108 H -3.693169 -1.503102 1.278254 C -4.473570 -3.146282 2.432970 H -5.320628 -2.573072 2.800361 C -4.312169 -4.478990 2.810443 H -5.031878 -4.951588 3.474345 C -3.219864 -5.204441 2.329954

12

H -3.083191 -6.244441 2.615520 C -2.295724 -4.595611 1.481421 H -1.450864 -5.173375 1.121032 C 4.379499 1.807795 -0.600305 C 5.535891 2.275433 0.044575 H 6.002467 1.683973 0.825822 C 6.083416 3.510400 -0.306539 H 6.975496 3.866539 0.201165 C 5.483200 4.286707 -1.300843 H 5.908336 5.249907 -1.569152 C 4.333963 3.824985 -1.945900 H 3.859894 4.426174 -2.716372 C 3.782048 2.590526 -1.598992 H 2.884117 2.241445 -2.098897 C 4.136372 -0.149585 1.563071 C 4.847490 -1.303692 1.914704 H 5.076763 -2.058078 1.171330 C 5.266767 -1.494045 3.234542 H 5.814658 -2.394797 3.496762 C 4.987352 -0.532582 4.204019 H 5.314399 -0.680960 5.229552 C 4.285336 0.625057 3.853495 H 4.059852 1.376022 4.605158 C 3.860127 0.820437 2.542219 H 3.297492 1.710705 2.286717 C 4.626410 -1.072329 -1.190384 C 4.110457 -2.371936 -1.328645 H 3.151496 -2.629357 -0.890130 C 4.828230 -3.333308 -2.039811 H 4.422263 -4.335871 -2.138563 C 6.054078 -3.006234 -2.624746 H 6.606861 -3.755546 -3.184765 C 6.565606 -1.714107 -2.493855 H 7.515255 -1.453098 -2.952441 C 5.857262 -0.747955 -1.776407 H 6.261773 0.254526 -1.684482 H 0.573933 -0.234936 -3.858517 H 2.652305 -0.223819 -2.724639 H -1.559573 -0.106186 -2.805360 O 1.261902 0.485741 1.439261 H 0.457497 0.490299 2.027726 N -1.400396 0.013069 1.906569 N -3.146740 -0.225681 -0.806364 C -1.573116 0.039878 3.079225 C -4.282537 -0.330538 -1.129844 S -1.812294 0.077003 4.703085 S -5.855359 -0.475741 -1.577790