Anette Yahav-Levi,a Israel Goldberga, Arkadi Vigalok … · S1 Supplementary Information Aryl-Bromide Reductive Elimination from an Isolated Pt(IV) Complex Anette Yahav-Levi,a Israel

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Supplementary Information

Aryl-Bromide Reductive Elimination from an Isolated Pt(IV) Complex

Anette Yahav-Levi,a Israel Goldberga, Arkadi Vigaloka* and Andrei N. Vedernikovb*

a- School of Chemistry, The Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv

University, Tel Aviv 69967, Israel. Tel: 972-3-6408617; E-mail: [email protected]

b- Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742,

USA. Tel: 1-301-405-2784; E-mail: [email protected]

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

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Experimental Section General procedures: All operations with air- and moisture- sensitive compounds were performed in a nitrogen-filled Innovative Technology glove box. All solvents were degassed and stored under high-purity nitrogen over activated 4Å molecular sieves. All deuterated solvents were stored under high-purity nitrogen on 3Å molecular sieves. Commercially available reagents (Aldrich and Strem) were used as received. The NMR spectra were recorded on Bruker AC 200MHz and Bruker AMX 400MHz spectrometers. 1H and 13C NMR signals are reported in ppm downfield from TMS. 1H signals are referenced to the residual proton of a deuterated solvent 7.26 ppm for CDCl3. 13C NMR signals are referenced to the solvent signal (CDCl3) at 77.36 ppm. 31P chemical shifts are reported in ppm downfield from H3PO3 and referenced to an external 85% phosphoric acid sample. 19F chemical shifts are reported in ppm downfield from CClF3. All measurements were performed at 22 ºC in CDCl3 unless stated otherwise. Elemental analysis was performed in the laboratory for microanalysis at the Hebrew University of Jerusalem. CCDC 763113-763115 contain full crystallographic data for complexes 1-3. Computational details. Theoretical calculations in this work have been performed using density functional theory (DFT) method,1 specifically functional PBE,2 implemented in a state-of-the-art program package “Priroda”.3,4 In PBE calculations relativistic Stevens-Basch-Krauss (SBK) effective core potentials (ECP)5 optimized for DFT-calculations have been used. Basis set was 311-split for main group elements with one additional polarization p-function for hydrogen, additional two polarization d-functions for elements of higher periods. Full geometry optimization has been performed without constraints on symmetry. For all species under investigation frequency analysis has been carried out. All minima have been checked for the absence of imaginary frequencies. All transition states possessed only one imaginary frequency. For all reactions where TS’s were located the transition states, corresponding reactants and products were proven to be connected by a single minimal energy reaction path. Method of Intrinsic Reaction Coordinate was used for this purpose. The Gibbs energy of solvation of the reactants and transition states in acetonitrile at 298K were calculated using a Poisson-Boltzmann continuum solvation model (PBF) implemented in the Jaguar program package.6 In these calculations geometries found with “Priroda” program package were used. If a geometry re-optimization was performed using the same functional PBE and LACVP relativistic basis set with two polarization functions the resulting solvation energies were within 0.1 kcal/mol. The experimental Gibbs solvation energy of Br- anion in MeCN of -69.2 kcal/mol was used.7


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Synthesis and characterization of compounds 1-3: Complex 1 The platinum complex 1 was prepared by an established ligand exchange protocol8 starting from (1,5-cyclooctadiene)Pt(4-C6H4F)C6F5 and (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxaline in toluene. 31P{1H} NMR (CDCl3), δ: 28.72 (br m, JPt-P= 2441.9 Hz), 31.19 (br d, JPt-P= 1649.6 Hz, JPa-Pb= 18.8 Hz ); 19F {1H} NMR (CDCl3), δ: -117.62 (br s, 1F), -120.40 (br s, 1F), -123.27 (s, 1F), -163.13 (s, 1F), -163.82 (s, 1F), -164.73 (s, 1F); 1H NMR (CDCl3), δ: 0.84 (br m, 18H), 1.89 (br m, 6H), 6.71 (br m, 2H), 7.25 (br m, 2H), 7.89 (br m, 2H), 8.22 (br m, 2H); 13C{1H} NMR (CDCl3), δ: 4.78 (m, JPaC= 26.5 Hz, JPbC= 308.3 Hz), 27.29 (m, JPC= 31.7 Hz), 34.68 (m, JPaC= 29.1 Hz, JPbC= 107.8 Hz), 113.98 (br s, Ar), 128.97 (m, J = 81.3 Hz, Ar), 130.35 (s, Ar), 132.70 (s, Ar), 135.81 (br m, Ar), 138.60 (br s, Ar), 142.08 (br s, Ar), 144.24 (br m, Ar), 146.23 (br m, Ar), 148.24 (br m, Ar), 157.68 (br m, Ar), 160.25 (d, JFC= 239.1 Hz, Ar). MS (FAB) calcd for C30H32F6N2P2Pt 791.6, found 790.9. X-ray structure data for 1: C30H32F6N2P2Pt, M= 791.61, 0.3 x 0.2 x 0.2 mm3, orthorhombic, space group P212121, a = 7.8934(2), b = 15.6326(5), c = 24.5087(9) Å, a=β =γ= 90°, V = 3024.24(17) Å3, Z = 4, ρcalcd. = 1.739 g.cm-3, θmax = 27.88º, Nonius KappaCCD, MoKα radiation (λ = 0.71073 Å), graphite monochromator, T = 110(2) K, 16709 collected reflections, 6644 unique reflections (Rint = 0.0600). R1 = 0.0467, wR2 = 0.1122 for data with I>2σ(I), and R1 = 0.0648, wR2 = 0.1227 for all unique data. Complex 2 Freshly prepared solution of Br2 (0.13 ml, 0.78 M in Benzene) was added dropwise (while stirring) to a solution of 1 (80 mg, 1 equiv) in CH2Cl2 (1 ml) at -30 ºC. After several minutes the 31P{1H} NMR spectrum showed the disappearance of the starting material and quantitative formation of 2. Five ml of pentane were added resulting in the product precipitation as a yellow powder (84 mg, 88 %). It was important to adhere to the exact stoichiometry to avoid formation of side products. 31P {1H} NMR (CDCl3), δ: -6.33 (s, JPtP= 929.1 Hz), -4.34 (s, JPtP= 1404.9 Hz); 19F{1H} NMR (CDCl3), δ: -102.80 (br s, 1F), -111.38 (br s, 1F), -121.10 (s, 1F), -160.21 (s, 1F), -163.04 (s, 1F), -165.35 (s, 1F); 1H NMR NMR (CDCl3), δ: 1.10 (br d, J= 15.5 Hz, 9H), 1.36 (br d, J= 15.1 Hz, 9H), 2.40 (br m, J= 10.5 Hz, 3H), 2.46 (br m, J= 9.7 Hz, 3H), 6.78 (br m, 2H), 8.00 (br m, 4H), 8.30 (br m, 2H); 13C{1H} NMR (CDCl3), δ: 4.88 (br m), 15.24 (br m), 27.72 (br-m, J= 17.6 Hz), 39.19 (m), 113.85 (br m, Ar), 122.56 (m, J= 139.7 Hz, Ar), 130.24 (s, Ar), 133.45 (s, Ar), 138.70 (br m, Ar), 141.36 (m, J= 141.7 Hz, Ar), 142.23 (m, J= 115.3, Ar), 148.81 (br m, Ar), 151.33 (br m, Ar), 154.34 (br m, Ar), 159.12 (m, Ar), 161.82 (d, JFC= 243.0 Hz, Ar). MS (FAB) calcd for C30H32Br2F6N2P2Pt 951.4, found 950.7. Elemental analysis for C30H32Br2F6N2P2Pt, Found (calc.): C 37.76 (37.87), H 3.37 (3.39). Complex 3


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A CD3CN solution of 2 (12 mg, 0.013 mmol) was warmed at 80 ºC in a sealed NMR tube. After 24hrs, complete disappearance of 2 was observed in 31P{1H} NMR spectrum, with the concomitant formation 3, p-FC6H4Br (80-90%, 19F NMR) and C6H5F (10-20%, 19F NMR). Evaporation of the volatiles gave 3 in a quantitative yield as a light-yellow powder. 31P{1H} NMR (CDCl3), δ: 30.53 (d, JPtP= 3623.2 Hz, JPP= 15.5 Hz), 30.75 (br s, JPtP= 2152.2 Hz); 19F{1H} NMR (CDCl3), δ: -114.10 (br s, 1F), -120.16 (br s, 1F), -161.28 (s, 1F), -162.76 (s, 1F), -164.42 (s, 1F); 1H NMR NMR (CDCl3), δ: 0.99 (m, J= 16.2 Hz, 9H), 1.19 (m, J= 15.3 Hz, 9H), 2.12 (m, J= 11.7 Hz, 3H), 2.26 (m, J= 10.4 Hz, 3H), 8.02 (m, 2H), 8.30 (m, 2H); 13C{1H} 6.01 (m, JPaC= 30.3 Hz, JPb-C= 230.6 Hz), 27.67 (m, J= 89.7 Hz), 35.75 (m), 130.43 (s, Ar), 133.37 (br s, Ar), 137.43 (br m, Ar), 139.46 (br m, Ar), 142.28 (s, Ar), 145.42 (br m, Ar), 147.75 (br m, Ar), 149.19 (br m, Ar), 154.99 (br m, Ar). MS (FAB) calcd for C24H28BrF5N2P2Pt 776.4, found 777.0. X-ray structure data for 3: C24H28BrF5N2P2Pt, M= 776.42, 0.25 x 0.20 x 0.10 mm3, monoclinic, space group P 21, a = 8.8747(3), b = 15.3391(5), c = 10.0545(4) Å, a=γ= 90°, β = 91.294(2), V = 1368.37(8) Å3, Z = 2, ρcalcd. = 1.884 g.cm-3, θmax = 27.84º, Nonius KappaCCD, MoKα radiation (λ = 0.71073 Å), graphite monochromator, T = 110(2) K, 14770 collected reflections, 6166 unique reflections (Rint = 0.0820). R1 = 0.0431, wR2 = 0.0851 for data with I>2σ(I), and R1 = 0.0653, wR2 = 0.0937 for all unique data. Kinetic Experiments: In a typical experiment, an NMR tube containing a freshly prepared CD3CN solution of 2 (12 mg, 0.013 mmol) was placed into the NMR probe preheated to 70 ºC. The reaction progress was followed by the 19F NMR spectroscopy which exhibited clean first-order reaction kinetics (see Fig. 1 below) up to about 70% conversion of the starting material. The first-order rate constant kobs=(1.64±0.01)·10-5 s-1 (average of three measurements) which corresponds to the reaction half-life 11.7h.

Figure S1. First-order kinetics plot for p-FC6H4-Br reductive elimination from complex 2 in CD3CN solution at 70oC.


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DFT-optimized geometries of complexes 1, 2, 3, 4, TSa and TSb

Total gas phase energy (E) is given in Hartrees; the gas-phase Gibbs energy correction (G), the

Gibbs solvation energy in MeCN (sfinal), both for 298K, are given in kcal/mol

Reaction Gibbs energies were calculated as Σ(E+G+sfinal)products - Σ(E+G+sfinal)reactants

Complex 1, E = -487.67567 G = 289.70

Pt 0.68409836 -0.23751480 -0.28017974 P -1.41537414 -0.47630468 0.75907500 P 0.15919816 2.00922513 -0.57590082 C -2.27060203 1.19113341 0.67761111 N -3.52154072 1.32700846 1.09542410 C -4.03541412 2.59100223 1.16117069 C -5.37541157 2.78796341 1.58656155 H -5.98119628 1.90931830 1.81240723 C -5.87015082 4.07275743 1.71730228 H -6.89862314 4.22819086 2.04669269 C -5.05190143 5.19947869 1.43388432 H -5.46390281 6.20277073 1.55248336 C -3.74758630 5.03658008 1.00402148 H -3.10621573 5.88648327 0.76680772 C -3.21878221 3.72884529 0.84401509 N -1.95395991 3.56155801 0.35574683 C -1.50210570 2.32109023 0.23525462 C 1.11337660 -2.28491078 -0.26042619 C 2.05211080 -2.87077176 0.59242951 C 2.39036953 -4.22721956 0.55251763 C 1.77390040 -5.06018051 -0.38631802 C 0.83038490 -4.51795391 -1.26305933 C 0.52592622 -3.15485251 -1.18135953 F 2.67888763 -2.11630752 1.53769127 F 3.29790729 -4.74649595 1.40619872 F 2.08256516 -6.37027054 -0.44275057 F 0.22980770 -5.31540008 -2.17362759 F -0.39801857 -2.68617181 -2.07548616 C 2.59807691 -0.01633328 -1.08503044 C 3.59000510 0.70517553 -0.38998472 H 3.35773143 1.16646970 0.57272993 C 4.89739169 0.83790351 -0.88305766 H 5.66106620 1.39237981 -0.33564056 C 5.21278810 0.24400013 -2.10203960 C 4.27453035 -0.49003235 -2.82311242 H 4.55867893 -0.95497863 -3.76816381 C 2.97879972 -0.62058300 -2.30168801 H 2.25551547 -1.21177286 -2.86781152 F 6.47782431 0.37868182 -2.59933277 C -2.68636963 -1.61056405 0.03360528


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H -3.68148182 -1.38839922 0.43976320 H -2.41053162 -2.65075823 0.25257831 H -2.68109025 -1.47766510 -1.05515208 C -1.40612396 -0.85539505 2.63932960 C -2.82432532 -1.04763722 3.20401303 H -3.31199110 -1.93964226 2.78557779 H -3.47200000 -0.18135972 3.01834669 H -2.75031477 -1.19600719 4.29411354 C -0.69402025 0.31426939 3.34575521 H -1.27715751 1.24595087 3.29879435 H 0.30122620 0.49527207 2.91263794 H -0.55839393 0.06463008 4.41034979 C -0.58878516 -2.14533310 2.84516927 H -0.62589612 -2.41694937 3.91290942 H 0.46235674 -2.00873761 2.56648477 H -0.99366640 -2.99541910 2.27659954 C 1.20149166 3.34480650 0.16893130 H 0.70406521 4.31900926 0.07859465 H 2.17895732 3.36183532 -0.32915725 H 1.35296369 3.10786788 1.23029818 C -0.12156572 2.52604722 -2.40124937 C -1.05075876 1.46805830 -3.02785149 H -1.18176199 1.68980889 -4.09923230 H -2.05040291 1.47190486 -2.56645096 H -0.62967853 0.45654066 -2.93166431 C 1.24970388 2.50158617 -3.10514024 H 1.74835241 1.52886090 -3.01544582 H 1.92690419 3.27499472 -2.71470469 H 1.09468212 2.71305532 -4.17570068 C -0.73686325 3.92857354 -2.54583475 H -0.10477660 4.70867404 -2.09873367 H -1.73729759 4.00402467 -2.10295713 H -0.82558188 4.15440422 -3.62150807

Complex 2, E = -514.46219 G = 292.17 sfinal: -11.53

Pt 0.81042562 -0.35975408 -0.35196946 Br 1.58769428 0.38460099 1.95453575 Br -0.07571815 -1.18337018 -2.59016050 P -1.51347000 -0.55657969 0.65208813 P 0.17920044 1.98215996 -0.76772617 C -2.15811002 1.20702412 0.72579474 N -3.34859693 1.40499123 1.27486527 C -3.79934779 2.68705833 1.38917727 C -5.06759561 2.94380646 1.97366934 H -5.67054004 2.09498224 2.29901408 C -5.49702925 4.24912805 2.12684034 H -6.46858964 4.45153542 2.58035288 C -4.68492969 5.33740236 1.70670368


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H -5.04626182 6.35774991 1.84365167 C -3.45031192 5.11603978 1.12510394 H -2.81459383 5.93611354 0.78846831 C -2.98818457 3.78553600 0.94665572 N -1.79214986 3.55547133 0.33340209 C -1.39247112 2.29839864 0.20110377 C 1.48849101 -2.33257057 0.07351715 C 2.78979543 -2.62108708 0.52426026 C 3.25492433 -3.92549295 0.74681932 C 2.41544087 -5.01765000 0.53243039 C 1.11056626 -4.77874500 0.10384347 C 0.68179714 -3.46427877 -0.10770505 F 3.69079026 -1.65422868 0.78481150 F 4.51719967 -4.13266172 1.16978386 F 2.84995205 -6.27213801 0.74360041 F 0.26362420 -5.81317973 -0.07977930 F -0.62711995 -3.34700963 -0.45766878 C 2.70816439 -0.00653465 -1.25408073 C 3.56960686 0.98047641 -0.75163432 H 3.31256776 1.53262789 0.15049753 C 4.81356415 1.23961587 -1.34530577 H 5.48178210 2.00367203 -0.94596342 C 5.19823972 0.48291393 -2.44763660 C 4.38962102 -0.53077774 -2.95143370 H 4.72508076 -1.12587685 -3.80168995 C 3.14607837 -0.77003794 -2.34856733 H 2.52521247 -1.56696791 -2.75401671 F 6.40369514 0.72955009 -3.03549424 C -2.82867819 -1.26789882 -0.44857248 H -3.81375187 -0.94623197 -0.08907705 H -2.76045446 -2.36078810 -0.45776152 H -2.64970390 -0.90669019 -1.46821068 C -1.89994419 -1.27074436 2.42080190 C -3.36532125 -1.74128555 2.50230339 H -3.58075844 -2.56616651 1.80987062 H -4.07076970 -0.92092241 2.31798935 H -3.54014080 -2.11770105 3.52383370 C -1.65244301 -0.20464503 3.50634041 H -2.38851575 0.60764845 3.45829992 H -0.64108042 0.21549430 3.44907695 H -1.76189460 -0.69165116 4.48924017 C -0.96585617 -2.47161548 2.65815209 H -1.17241121 -2.87391829 3.66331291 H 0.09221377 -2.18232793 2.61957980 H -1.14362691 -3.28073914 1.93788517 C 1.29237162 3.26815041 -0.04555142 H 0.71051811 4.19020280 0.07652768 H 2.14582222 3.44070274 -0.71177704 H 1.64727368 2.91258250 0.92929948 C -0.20461215 2.66283308 -2.52818107 C -1.55130223 2.09801762 -3.01750408 H -1.71586590 2.43455765 -4.05402073


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H -2.39327202 2.47219036 -2.41659928 H -1.56001147 1.00078397 -3.01661515 C 0.94788310 2.22361167 -3.45295780 H 1.00076701 1.13300181 -3.55285968 H 1.92344678 2.59075458 -3.10168961 H 0.77285094 2.65618281 -4.45179625 C -0.28021697 4.20337852 -2.50863830 H 0.69079533 4.66553614 -2.28624871 H -1.02395042 4.57923118 -1.79423410 H -0.57585465 4.53405197 -3.51787746 Complex 3, E = -440.42943 G = 243.37 Pt -1.11920869 0.27590102 -1.06591684 Br -2.64598576 1.88705950 -2.25939018 P 0.44012528 -1.04931705 -0.07402213 P -0.95181981 1.72329808 0.75468795 C 0.87754568 -0.27584365 1.57771735 N 1.68052747 -0.91677492 2.41380876 C 2.10735813 -0.23789062 3.52079272 C 2.95883278 -0.87888138 4.45811631 H 3.21821963 -1.92531799 4.29176347 C 3.44668092 -0.16619377 5.53831199 H 4.10556105 -0.65388209 6.25818564 C 3.10637014 1.20129795 5.72121785 H 3.50977095 1.74174499 6.57876206 C 2.26664333 1.84665401 4.83196426 H 1.97869101 2.89088065 4.96059273 C 1.73795652 1.13596391 3.72263460 N 0.85073710 1.74999547 2.88408808 C 0.39652109 1.04676099 1.85625905 C -1.53708264 -1.09523527 -2.59349059 C -2.36571310 -2.19376811 -2.35402703 C -2.78106409 -3.08039749 -3.35340022 C -2.35727503 -2.87346160 -4.66851927 C -1.52672980 -1.78593363 -4.95503157 C -1.14145536 -0.92440666 -3.92291657 F -0.32434695 0.10612161 -4.26712647 F -1.10734730 -1.58654093 -6.22219475 F -2.73923563 -3.71559266 -5.64766953 F -3.58464383 -4.12781050 -3.06749811 F -2.82533966 -2.44706333 -1.09238491 C -0.00102550 -2.78510766 0.37782225 H 0.73702148 -3.18823098 1.08314273 H -0.03669850 -3.39964063 -0.53109831 H -0.99915953 -2.77901093 0.83095948 C -0.46616320 3.48261963 0.48559800 H -0.38681344 4.02829390 1.43441575 H -1.21357315 3.94162576 -0.17446920 H 0.50414644 3.49098184 -0.02772178


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C 2.13693245 -1.15128071 -0.96076456 C 2.72946372 0.27048230 -1.00119888 H 3.00162592 0.63795375 -0.00076171 H 2.02980733 0.98214300 -1.46383316 H 3.64848473 0.25894049 -1.60843363 C 1.90332240 -1.64673435 -2.39977570 H 2.88564517 -1.79290466 -2.87775638 H 1.34280496 -0.91767454 -2.99448052 H 1.37509436 -2.61057354 -2.43558429 C 3.09248232 -2.11770291 -0.23587282 H 4.07141629 -2.07694542 -0.74080779 H 2.73991892 -3.15741003 -0.29041169 H 3.23957846 -1.85743038 0.81972592 C -2.49661052 1.74232409 1.89504429 C -2.21613877 2.40619280 3.25464395 H -3.16404271 2.44438964 3.81645794 H -1.85458601 3.43883775 3.15221579 H -1.49067426 1.84939956 3.86020623 C -2.92769916 0.27662430 2.09715130 H -3.83419239 0.25167330 2.72303663 H -2.15613649 -0.31556533 2.61329513 H -3.15575441 -0.21224352 1.13925291 C -3.61317063 2.52016502 1.17179981 H -3.81859777 2.12276328 0.16934669 H -3.37021670 3.58806012 1.07225861 H -4.53178521 2.44511854 1.77628237 p-FC6H4Br E = -74.061327 G = 29.67 Br 3.18214768 0.59667926 0.11243904 F -2.74223442 -0.51434309 -0.09746551 C 1.30004719 0.24391858 0.04649512 C 0.42165001 1.27980789 -0.28738669 H 0.80055923 2.27717678 -0.50727227 C -0.95338340 1.02243023 -0.33604359 H -1.66529053 1.80669220 -0.59309857 C -1.40815060 -0.26397156 -0.04949941 C -0.53936480 -1.30230581 0.28340604 H -0.93502625 -2.29416178 0.50164781 C 0.83549436 -1.04400579 0.33209711 H 1.53379048 -1.83974636 0.58870283 Complex 4, E = -500.80564 G = 290.24 sfinal: -37.58 Pt 1.19668566 -0.60670247 -0.00678764 Br 2.01371884 0.35401304 2.17252009 P -1.12822709 -0.89153981 0.82351866


S10

P 0.52436452 1.63884273 -0.51356349 C -1.85039610 0.83135865 0.86120275 N -3.06131360 1.00213025 1.37200563 C -3.54026136 2.27579033 1.46609009 C -4.82923411 2.50882136 2.01144503 H -5.42535364 1.65194664 2.32673137 C -5.28945089 3.80644806 2.13798497 H -6.27823628 3.99248946 2.55915923 C -4.48939143 4.90967845 1.73083868 H -4.87842390 5.92186907 1.84820036 C -3.23322402 4.71408123 1.18774224 H -2.60799072 5.54662283 0.86371168 C -2.73731466 3.39324362 1.03656011 N -1.51590788 3.18585747 0.46684107 C -1.09017217 1.93532045 0.36665528 C 1.63814736 -2.66886485 0.06107433 C 2.65048478 -3.25516570 0.84130438 C 2.93499258 -4.62568302 0.81074881 C 2.20738668 -5.46330639 -0.04325529 C 1.20495394 -4.91548224 -0.85970288 C 0.94950960 -3.54657641 -0.78469230 F 3.38011019 -2.51089872 1.69297283 F 3.89642672 -5.14457804 1.58417779 F 2.47556178 -6.76783642 -0.09881427 F 0.53213245 -5.70402276 -1.70918611 F 0.00691972 -3.05095888 -1.64119969 C 3.06968983 -0.44014156 -0.88804414 C 4.03657039 0.53019107 -0.53769031 H 3.91019442 1.13426095 0.36004049 C 5.16416136 0.73383191 -1.33066706 H 5.90589580 1.49415320 -1.08372896 C 5.33823156 -0.05812412 -2.47469063 C 4.43407263 -1.06073149 -2.82747925 H 4.61420282 -1.67233789 -3.71173897 C 3.32634110 -1.27939609 -2.00307701 H 2.64663631 -2.08898989 -2.26447785 F 6.42353157 0.14367135 -3.24189567 C -2.30304213 -1.76035070 -0.31712616 H -3.33212872 -1.52747103 -0.01650743 H -2.13444030 -2.84277449 -0.26803495 H -2.12712895 -1.43010891 -1.34640768 C -1.47357694 -1.65653176 2.56249206 C -2.93267793 -2.15003381 2.63812532 H -3.13586338 -2.97903081 1.94738840 H -3.65191981 -1.34144956 2.45607703 H -3.10190593 -2.52983556 3.65826331 C -1.23128726 -0.61131573 3.66685047 H -1.97498832 0.19542878 3.63632794 H -0.22549084 -0.17648055 3.62116685 H -1.33330757 -1.11573398 4.64058225 C -0.51083600 -2.84559892 2.73651235 H -0.75039445 -3.34828654 3.68671412


S11

H 0.53661302 -2.52155137 2.78302247 H -0.61662095 -3.59323994 1.93638188 C 1.55319776 3.08121246 -0.02073210 H 0.93421923 3.98407421 -0.10676672 H 2.43500834 3.15629589 -0.66788120 H 1.86817803 2.95015745 1.02124296 C 0.16272838 1.84760687 -2.38739076 C -0.75795535 0.69919883 -2.83789224 H -0.96297374 0.80852494 -3.91409009 H -1.72822023 0.72101814 -2.32039599 H -0.29478793 -0.28806540 -2.68891523 C 1.49609603 1.79354895 -3.15546569 H 2.02944371 0.84635917 -3.00914369 H 2.16596348 2.62258692 -2.88962055 H 1.27436806 1.88943052 -4.22994157 C -0.52142373 3.20572039 -2.63589500 H 0.10942733 4.05501153 -2.34177427 H -1.48794101 3.29691847 -2.12584556 H -0.70395045 3.29334453 -3.71928695 Br-, E = -13.45746 G = -6.9 sfinal: -74.99; exp. Value of -69.2 was used7 TSa, E = -514.39658 G = 291.8 sfinal: -15.53 Pt 0.82741199 -0.43403118 1.06351407 Br 1.99845902 2.03679115 1.35030261 Br 1.81705426 -2.89691770 1.06644430 P -1.50069909 0.01178748 0.77424305 P 0.98386483 -0.20998873 -1.38260173 C -1.86722970 -0.03453870 -1.05048003 N -3.12998601 -0.05119704 -1.45312441 C -3.37118746 0.12093574 -2.78525442 C -4.70161922 0.08197804 -3.27861030 H -5.50792366 -0.14574245 -2.58016609 C -4.94215173 0.34845829 -4.61402156 H -5.96335036 0.32472289 -4.99728633 C -3.87450085 0.66429834 -5.49752630 H -4.09325081 0.87867495 -6.54463840 C -2.56747454 0.69382111 -5.04706304 H -1.73214674 0.91773556 -5.71185682 C -2.28869309 0.40364727 -3.68548721 N -0.99637029 0.35788948 -3.24928065 C -0.78048991 0.08143813 -1.97181588 C 0.29574581 -0.85275057 3.09712662 C 0.53982482 -0.02947708 4.20988718 C 0.20994915 -0.36208976 5.53103017


S12

C -0.42439967 -1.57102009 5.80665358 C -0.72307292 -2.41488634 4.73777902 C -0.37542211 -2.04726048 3.43147846 F 1.13078064 1.18588436 4.08065888 F 0.50115327 0.48567392 6.53876069 F -0.75288261 -1.90809063 7.06544667 F -1.36542693 -3.57729805 4.96944946 F -0.77779485 -2.92841483 2.48826208 C 3.14735164 0.03440707 1.52413562 C 4.05780636 -0.04519386 0.45831669 H 3.78232158 0.30091370 -0.53384408 C 5.34073009 -0.55780255 0.66091344 H 6.04554685 -0.65305698 -0.16549767 C 5.71642012 -0.93692605 1.94885908 C 4.85464285 -0.79377149 3.03391820 H 5.18154275 -1.07907040 4.03402657 C 3.57119966 -0.27956097 2.82480350 H 2.91916200 -0.15377821 3.68227643 F 6.96677488 -1.43149050 2.15364244 C -2.79538036 -1.13479893 1.42590671 H -3.75223306 -0.88015383 0.95444869 H -2.86848768 -1.04067409 2.51641788 H -2.51214587 -2.16141032 1.17400360 C -2.14222109 1.77175067 1.24401979 C -3.67911664 1.84101843 1.16829972 H -4.15829836 1.22784935 1.94380874 H -4.06948416 1.53528143 0.18860649 H -3.98154684 2.88653135 1.34438903 C -1.52238121 2.78937358 0.26777134 H -1.91414674 2.67840301 -0.75368280 H -0.42563154 2.71669754 0.24579479 H -1.77953993 3.80569269 0.60749606 C -1.68668815 2.08198668 2.68027926 H -2.10376393 3.05931356 2.97386959 H -0.59518151 2.14347056 2.75870764 H -2.05536417 1.33842049 3.40199523 C 1.79445980 1.29426591 -2.11025283 H 1.32771970 1.50297826 -3.08153771 H 2.86935976 1.12365188 -2.25246769 H 1.66187441 2.13865266 -1.42374739 C 1.56529851 -1.65007341 -2.53678886 C 0.60343150 -2.83573744 -2.33263008 H 0.96971169 -3.69025785 -2.92438032 H -0.41135707 -2.60374760 -2.68954436 H 0.56241227 -3.14939555 -1.28053790 C 3.00550805 -2.03363479 -2.14697043 H 3.08841449 -2.32742346 -1.09369137 H 3.71336486 -1.21904179 -2.36186444 H 3.30680216 -2.89292333 -2.76876837 C 1.56979526 -1.22814561 -4.01941778 H 2.28470683 -0.41789000 -4.22024004 H 0.58305017 -0.91974448 -4.38101781


S13

H 1.89613485 -2.10264339 -4.60639927 TSb E = -500.80028 G = 291.70 sfinal: -38.00 Pt -1.03426711 0.00346053 0.90509752 Br -2.36124472 -2.15360098 0.77791518 P 1.35974829 -0.36857200 0.83197891 P -0.84325741 0.32615387 -1.48453437 C 1.89943988 -0.19288027 -0.94141285 N 3.19101128 -0.24052420 -1.23187580 C 3.54107554 -0.29866536 -2.54930548 C 4.91064275 -0.33993546 -2.91772367 H 5.66482238 -0.28025081 -2.13239864 C 5.25156214 -0.47142440 -4.25113961 H 6.30235753 -0.50976864 -4.54101779 C 4.25002450 -0.56661758 -5.25651020 H 4.55080185 -0.67690243 -6.29911712 C 2.90751043 -0.51275313 -4.93010261 H 2.12630405 -0.56909307 -5.68885767 C 2.52622149 -0.36227890 -3.57182819 N 1.20835298 -0.23275037 -3.24293757 C 0.90376255 -0.11610020 -1.95943762 C -0.80116974 0.24488473 3.00250392 C -1.05531575 -0.62812585 4.06566985 C -0.87617335 -0.26099374 5.40806004 C -0.44409752 1.03064078 5.72717500 C -0.20124139 1.94327060 4.69404660 C -0.38761056 1.52797586 3.37354042 F -1.51827149 -1.87994218 3.84892175 F -1.12427152 -1.13829428 6.39098392 F -0.27383189 1.39252634 7.00260973 F 0.19488432 3.19325004 4.97803478 F -0.17166954 2.46413418 2.39605587 C -3.13492788 0.33560153 1.08291331 C -3.97993717 0.37399026 -0.05501353 H -3.65171792 -0.05898431 -0.99590035 C -5.24139848 0.95749399 0.00509472 H -5.88260079 1.02785960 -0.87343327 C -5.69517112 1.43208926 1.24050601 C -4.93641084 1.30673701 2.40978905 H -5.34028415 1.65609940 3.36007797 C -3.68015559 0.70879396 2.33566356 H -3.11334264 0.57715240 3.25281640 F -6.91429718 1.98536475 1.31373391 C 2.46071156 0.79688193 1.74293101 H 3.48500310 0.67659752 1.36773022 H 2.42562123 0.57803772 2.81779028 H 2.12027639 1.82491299 1.57366249 C 1.94526628 -2.14630212 1.28253279


S14

C 3.48490505 -2.17091644 1.36242438 H 3.86363814 -1.58617719 2.21170052 H 3.96579785 -1.81438636 0.44315471 H 3.79173611 -3.21655622 1.52446537 C 1.44468599 -3.10821254 0.18931422 H 1.93235359 -2.93148523 -0.77950965 H 0.35414232 -3.05524991 0.06006450 H 1.68989278 -4.13741756 0.49401636 C 1.35268091 -2.54345807 2.64286732 H 1.77200971 -3.52225622 2.92449006 H 0.26299933 -2.64645791 2.60386315 H 1.62014348 -1.83588189 3.44088142 C -1.83921559 -0.62378907 -2.71734738 H -1.23405787 -0.73112675 -3.62793940 H -2.77094523 -0.09828702 -2.96139968 H -2.07243214 -1.61307761 -2.30183813 C -0.93281457 2.18725101 -1.98626032 C 0.19580454 2.93381502 -1.24898287 H 0.11814382 4.00665185 -1.48371231 H 1.19628173 2.60581147 -1.56386031 H 0.11342431 2.83170646 -0.15701573 C -2.29131193 2.77048183 -1.56350724 H -2.43876574 2.74354129 -0.47657086 H -3.13658455 2.26347202 -2.04944486 H -2.32334928 3.82484375 -1.88057880 C -0.76930800 2.32490887 -3.51128708 H -1.60468608 1.86981568 -4.06105787 H 0.16674288 1.89072453 -3.88282278 H -0.76427143 3.39918108 -3.75626528 Br2 E = -26.755778 G = -15.13 Br -7.04825064 2.68544829 0.00000000 Br -4.73641736 2.39646071 0.00000000 Br E = -13.334774 G = -6.9 A product of one Br atom loss from 2, E = -501.05163 G = 289.58 Pt 1.16611473 -0.62890151 -0.03575876 Br 2.00677574 0.41287715 2.33880002 P -1.07086000 -0.88801048 0.87342867 P 0.52490789 1.59855439 -0.55410982 C -1.83936582 0.82193722 0.86448475 N -3.05259660 0.98928759 1.37050596


S15

C -3.53734197 2.26365646 1.45001218 C -4.82930867 2.49602626 1.99023372 H -5.42035695 1.63599748 2.30774649 C -5.29650906 3.79177126 2.11323325 H -6.28706372 3.97471329 2.53235785 C -4.49825352 4.89474382 1.70629044 H -4.88811734 5.90740325 1.81967938 C -3.24036134 4.69713763 1.16700427 H -2.61392009 5.52791100 0.83968721 C -2.73953563 3.37725615 1.01860602 N -1.51982643 3.17482130 0.43906301 C -1.08514631 1.92693231 0.34358131 C 1.62564889 -2.68302647 0.06250756 C 2.53396534 -3.29701566 0.93197120 C 2.82263531 -4.66727783 0.88950561 C 2.19973571 -5.48121287 -0.06086544 C 1.29937148 -4.90662379 -0.96101184 C 1.04318927 -3.53513274 -0.87856397 F 3.17890118 -2.58132305 1.87849883 F 3.69708132 -5.21550341 1.75667587 F 2.46827270 -6.79878849 -0.11299360 F 0.69880015 -5.67489680 -1.89524919 F 0.17403942 -3.02751907 -1.81148776 C 3.00671808 -0.43732354 -1.01287208 C 4.04125928 0.39032097 -0.53919985 H 3.92244522 0.92123129 0.40696138 C 5.24554717 0.53093298 -1.24359063 H 6.04935582 1.16827065 -0.87234311 C 5.40897932 -0.16556135 -2.43872153 C 4.41968408 -1.00931854 -2.93740266 H 4.58424998 -1.55175563 -3.86917871 C 3.22792754 -1.14768042 -2.21074645 H 2.46373970 -1.81861073 -2.60845023 F 6.57369802 -0.02668074 -3.13431046 C -2.21740466 -1.80219266 -0.26683519 H -3.26285716 -1.62030364 0.01193568 H -1.99760056 -2.87637153 -0.21577770 H -2.03489044 -1.46673640 -1.29384950 C -1.45560296 -1.61333430 2.61889712 C -2.89522738 -2.15855770 2.68418408 H -3.05593910 -3.00815208 2.00631637 H -3.63865659 -1.38007297 2.46731722 H -3.07481680 -2.52163242 3.70948335 C -1.26743078 -0.53624942 3.70368518 H -2.04841585 0.23374772 3.65169777 H -0.28025961 -0.05961399 3.64223271 H -1.34780462 -1.02500710 4.68845606 C -0.44927372 -2.75858150 2.84238464 H -0.68066522 -3.24359877 3.80469848 H 0.58145385 -2.38421014 2.88664874 H -0.51075346 -3.52897883 2.05933205 C 1.57265420 3.02697581 -0.04804148


S16

H 1.01259285 3.96233775 -0.17276981 H 2.48864590 3.03721446 -0.65148378 H 1.83931651 2.87735835 1.00607857 C 0.10895094 1.89886571 -2.40322482 C -0.76786026 0.72969135 -2.88738610 H -0.97461131 0.85262576 -3.96261965 H -1.73867483 0.70296218 -2.36937833 H -0.26698605 -0.23990065 -2.74830332 C 1.44050942 1.91034544 -3.18128300 H 2.03163231 1.00075182 -3.01549078 H 2.06028784 2.77997300 -2.92174748 H 1.21387129 1.97920982 -4.25751787 C -0.62379072 3.23329235 -2.62821846 H -0.04392993 4.09407314 -2.26811465 H -1.61063125 3.26115336 -2.14946659 H -0.77190558 3.36516113 -3.71295047 Nucleophilic attack of Br- at the bromo ligand in 4 in MeCN solution was found to be barrierless.


S17

Crystallographic details

Complex 3 Crystal data

C24H28BrF5N2P2Pt

Mr = 776.42 Dx = 1.884 Mg m−3

Monoclinic, P21 Melting point: ? K

Hall symbol: ? Mo Kα radiation, λ = 0.71073 Å

a = 8.8747 (3) Å Cell parameters from 2350 reflections

b = 15.3391 (5) Å θ = 2.4–27.8°

c = 10.0545 (4) Å µ = 6.75 mm−1

β = 91.294 (2)° T = 110 K

V = 1368.37 (8) Å3 Prism, yellow

Z = 2 0.25 × 0.20 × 0.10 mm

F(000) = 748

Data collection

Nonius KappaCCD diffractometer 6166 independent reflections

Radiation source: fine-focus sealed tube 4989 reflections with I > 2σ(I)

graphite Rint = 0.082

Detector resolution: 12.8 pixels mm-1 θmax = 27.8°, θmin = 2.4°

1 deg. ω scans h = −11 11

Absorption correction: multi-scan Blessing, 1995 k = −19 19

Tmin = 0.283, Tmax = 0.552 l = −13 13

14770 measured reflections


S18

Refinement

Refinement on F2 Hydrogen site location: inferred from neighbouring sites

Least-squares matrix: full H-atom parameters constrained

R[F2 > 2σ(F2)] = 0.043 w = 1/[σ2(Fo2) + (0.041P)2 + 0.4117P]

where P = (Fo2 + 2Fc

2)/3

wR(F2) = 0.094 (Δ/σ)max = 0.003

S = 1.03 Δρmax = 1.64 e Å−3

6166 reflections Δρmin = −1.72 e Å−3

324 parameters Extinction correction: none

1 restraint Extinction coefficient: ?

? constraints Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881

Primary atom site location: structure-invariant direct methods Flack parameter: −0.015 (9)

Secondary atom site location: difference Fourier map

Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

The peripheral aromatic fragments exhibit large-amplitude thermal motion.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

Pt1 0.38500 (3) 0.12614 (2) 0.13199 (3) 0.03121 (9)

Br2 0.22102 (12) 0.23129 (7) 0.00939 (11) 0.0482 (3)

P3 0.5505 (2) 0.03899 (15) 0.2386 (2) 0.0305 (5)

P4 0.3929 (2) 0.21582 (15) 0.3125 (2) 0.0323 (5)

C5 0.6044 (9) 0.0931 (6) 0.3960 (9) 0.032 (2)


S19

N6 0.7012 (8) 0.0532 (5) 0.4783 (7) 0.0325 (16)

C7 0.7554 (10) 0.1033 (5) 0.5795 (8) 0.034 (2)

C8 0.8656 (10) 0.0661 (6) 0.6735 (9) 0.039 (2)

H8 0.8925 0.0063 0.6674 0.047*

C9 0.9291 (8) 0.1168 (9) 0.7693 (8) 0.041 (2)

H9 1.0036 0.0929 0.8280 0.050*

C10 0.8860 (10) 0.2051 (8) 0.7830 (9) 0.052 (3)

H10 0.9320 0.2394 0.8514 0.062*

C11 0.7804 (9) 0.2422 (6) 0.7010 (9) 0.040 (2)

H11 0.7514 0.3013 0.7126 0.049*

C12 0.7149 (9) 0.1916 (6) 0.5984 (8) 0.0329 (19)

N13 0.6025 (7) 0.2276 (5) 0.5183 (7) 0.0315 (15)

C14 0.5494 (9) 0.1778 (6) 0.4215 (9) 0.030 (2)

C15 0.3440 (9) 0.0413 (6) −0.0267 (9) 0.0321 (19)

C16 0.2464 (10) −0.0262 (8) −0.0142 (9) 0.044 (2)

C17 0.1924 (10) −0.0782 (7) −0.1204 (10) 0.048 (2)

C18 0.2421 (10) −0.0586 (6) −0.2459 (9) 0.041 (2)

C19 0.3447 (10) 0.0055 (7) −0.2619 (8) 0.041 (2)

C20 0.3931 (9) 0.0569 (6) −0.1538 (8) 0.0354 (19)

F21 0.4908 (4) 0.1216 (5) −0.1778 (4) 0.0450 (11)

F22 0.4030 (6) 0.0213 (5) −0.3833 (5) 0.0537 (14)

F23 0.1977 (7) −0.1073 (4) −0.3512 (6) 0.0621 (16)

F24 0.0921 (6) −0.1451 (4) −0.1002 (6) 0.0559 (16)

F25 0.1923 (6) −0.0488 (4) 0.1077 (5) 0.0459 (13)

C26 0.4844 (11) −0.0669 (6) 0.2897 (10) 0.041 (2)

H26A 0.5550 −0.0916 0.3560 0.062*

H26B 0.4776 −0.1056 0.2123 0.062*

H26C 0.3847 −0.0610 0.3287 0.062*


S20

C27 0.4301 (13) 0.3303 (7) 0.2870 (12) 0.051 (3)

H27A 0.4497 0.3585 0.3732 0.077*

H27B 0.3424 0.3576 0.2430 0.077*

H27C 0.5184 0.3370 0.2311 0.077*

C28 0.7356 (9) 0.0212 (6) 0.1548 (9) 0.038 (2)

C29 0.8126 (9) 0.1104 (8) 0.1452 (9) 0.048 (3)

H29A 0.8333 0.1331 0.2349 0.073*

H29B 0.7462 0.1509 0.0964 0.073*

H29C 0.9075 0.1043 0.0981 0.073*

C30 0.7067 (10) −0.0143 (7) 0.0147 (9) 0.043 (2)

H30A 0.8029 −0.0293 −0.0254 0.064*

H30B 0.6552 0.0301 −0.0396 0.064*

H30C 0.6433 −0.0665 0.0192 0.064*

C31 0.8333 (10) −0.0442 (8) 0.2318 (10) 0.053 (3)

H31A 0.9292 −0.0519 0.1867 0.079*

H31B 0.7808 −0.1003 0.2359 0.079*

H31C 0.8528 −0.0225 0.3222 0.079*

C32 0.2211 (9) 0.2072 (6) 0.4151 (9) 0.039 (2)

C33 0.2535 (10) 0.2341 (7) 0.5604 (9) 0.046 (2)

H33A 0.1589 0.2355 0.6087 0.070*

H33B 0.2998 0.2921 0.5625 0.070*

H33C 0.3224 0.1919 0.6024 0.070*

C34 0.1645 (9) 0.1133 (9) 0.4098 (9) 0.047 (3)

H34A 0.0784 0.1070 0.4684 0.071*

H34B 0.2455 0.0739 0.4393 0.071*

H34C 0.1333 0.0988 0.3184 0.071*

C35 0.0972 (11) 0.2669 (8) 0.3565 (11) 0.062 (3)

H35A 0.0752 0.2502 0.2640 0.093*


S21

H35B 0.1317 0.3276 0.3596 0.093*

H35C 0.0058 0.2610 0.4086 0.093*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Pt1 0.02985 (13) 0.03342 (15) 0.02999 (14) −0.0024 (2) −0.00731 (9) 0.0009 (2)

Br2 0.0498 (6) 0.0454 (6) 0.0484 (6) 0.0088 (5) −0.0249 (5) −0.0015 (5)

P3 0.0318 (10) 0.0314 (12) 0.0281 (11) 0.0006 (9) −0.0046 (9) 0.0014 (9)

P4 0.0307 (10) 0.0323 (12) 0.0335 (12) −0.0025 (9) −0.0093 (9) −0.0009 (10)

C5 0.026 (4) 0.032 (5) 0.037 (5) 0.001 (3) −0.001 (4) 0.002 (3)

N6 0.035 (4) 0.037 (4) 0.026 (4) 0.004 (3) −0.004 (3) 0.001 (3)

C7 0.043 (4) 0.042 (7) 0.018 (4) 0.015 (4) 0.004 (3) 0.011 (3)

C8 0.047 (5) 0.040 (5) 0.030 (5) 0.009 (4) −0.005 (4) 0.020 (4)

C9 0.032 (4) 0.058 (7) 0.035 (4) −0.002 (6) 0.000 (3) 0.000 (6)

C10 0.033 (5) 0.090 (9) 0.031 (5) 0.004 (5) −0.012 (4) −0.005 (5)

C11 0.037 (5) 0.041 (5) 0.043 (5) 0.002 (4) −0.007 (4) −0.009 (4)

C12 0.036 (4) 0.047 (5) 0.015 (4) −0.004 (4) −0.001 (3) −0.002 (4)

N13 0.026 (3) 0.035 (4) 0.034 (4) −0.004 (3) −0.002 (3) −0.004 (3)

C14 0.028 (4) 0.033 (5) 0.030 (5) 0.000 (4) −0.003 (4) −0.002 (4)

C15 0.028 (4) 0.029 (5) 0.040 (5) 0.007 (3) 0.004 (4) 0.011 (4)

C16 0.035 (5) 0.068 (7) 0.027 (5) −0.003 (5) −0.007 (4) 0.006 (5)

C17 0.035 (5) 0.062 (7) 0.046 (6) −0.008 (5) −0.003 (4) −0.010 (5)

C18 0.037 (5) 0.051 (6) 0.035 (5) 0.004 (4) −0.008 (4) −0.022 (4)

C19 0.041 (5) 0.060 (6) 0.023 (4) 0.011 (5) 0.001 (4) 0.002 (4)

C20 0.034 (4) 0.043 (5) 0.029 (5) 0.000 (4) −0.006 (4) 0.007 (4)

F21 0.042 (2) 0.052 (3) 0.041 (2) −0.011 (4) −0.0017 (19) 0.014 (4)

F22 0.060 (3) 0.071 (4) 0.029 (3) 0.007 (3) −0.003 (3) 0.004 (3)

F23 0.061 (4) 0.074 (4) 0.051 (4) −0.005 (3) −0.012 (3) −0.029 (3)


S22

F24 0.055 (3) 0.053 (4) 0.059 (4) −0.025 (3) 0.001 (3) −0.019 (3)

F25 0.045 (3) 0.063 (4) 0.030 (3) −0.017 (3) 0.006 (2) −0.007 (2)

C26 0.053 (6) 0.036 (5) 0.034 (5) −0.003 (5) −0.011 (4) 0.001 (4)

C27 0.061 (7) 0.029 (5) 0.063 (7) −0.009 (5) −0.016 (6) −0.002 (5)

C28 0.028 (4) 0.036 (5) 0.049 (5) 0.004 (4) −0.006 (4) −0.003 (4)

C29 0.033 (4) 0.070 (8) 0.043 (5) −0.013 (5) 0.006 (3) 0.001 (5)

C30 0.040 (5) 0.057 (6) 0.032 (5) 0.010 (4) 0.003 (4) −0.002 (4)

C31 0.038 (5) 0.075 (7) 0.045 (6) 0.020 (5) 0.000 (4) −0.003 (5)

C32 0.029 (4) 0.041 (5) 0.046 (5) 0.002 (4) −0.006 (4) −0.006 (4)

C33 0.041 (5) 0.052 (6) 0.046 (6) −0.004 (5) 0.003 (4) −0.018 (5)

C34 0.038 (4) 0.066 (8) 0.039 (4) −0.003 (6) −0.003 (3) −0.010 (6)

C35 0.045 (6) 0.071 (8) 0.070 (8) 0.009 (5) −0.001 (5) 0.007 (6)

Geometric parameters (Å, °)

Pt1—C15 2.084 (9) C19—F22 1.358 (9)

Pt1—P3 2.241 (2) C19—C20 1.403 (13)

Pt1—P4 2.277 (2) C20—F21 1.343 (10)

Pt1—Br2 2.4815 (10) C26—H26A 0.9800

P3—C26 1.806 (10) C26—H26B 0.9800

P3—C5 1.841 (9) C26—H26C 0.9800

P3—C28 1.883 (8) C27—H27A 0.9800

P4—C27 1.806 (10) C27—H27B 0.9800

P4—C14 1.844 (9) C27—H27C 0.9800

P4—C32 1.865 (9) C28—C31 1.525 (13)

C5—N6 1.329 (11) C28—C30 1.526 (12)

C5—C14 1.412 (12) C28—C29 1.534 (14)

N6—C7 1.355 (11) C29—H29A 0.9800

C7—C12 1.415 (13) C29—H29B 0.9800


S23

C7—C8 1.461 (12) C29—H29C 0.9800

C8—C9 1.351 (14) C30—H30A 0.9800

C8—H8 0.9500 C30—H30B 0.9800

C9—C10 1.416 (17) C30—H30C 0.9800

C9—H9 0.9500 C31—H31A 0.9800

C10—C11 1.359 (13) C31—H31B 0.9800

C10—H10 0.9500 C31—H31C 0.9800

C11—C12 1.406 (12) C32—C34 1.526 (16)

C11—H11 0.9500 C32—C33 1.538 (12)

C12—N13 1.383 (11) C32—C35 1.538 (14)

N13—C14 1.316 (10) C33—H33A 0.9800

C15—C16 1.358 (13) C33—H33B 0.9800

C15—C20 1.380 (12) C33—H33C 0.9800

C16—F25 1.370 (10) C34—H34A 0.9800

C16—C17 1.408 (14) C34—H34B 0.9800

C17—F24 1.377 (11) C34—H34C 0.9800

C17—C18 1.380 (14) C35—H35A 0.9800

C18—F23 1.347 (10) C35—H35B 0.9800

C18—C19 1.353 (13) C35—H35C 0.9800

C15—Pt1—P3 95.5 (2) C15—C20—C19 121.5 (8)

C15—Pt1—P4 171.4 (2) P3—C26—H26A 109.5

P3—Pt1—P4 88.34 (8) P3—C26—H26B 109.5

C15—Pt1—Br2 86.3 (2) H26A—C26—H26B 109.5

P3—Pt1—Br2 174.86 (7) P3—C26—H26C 109.5

P4—Pt1—Br2 90.60 (6) H26A—C26—H26C 109.5

C26—P3—C5 103.9 (4) H26B—C26—H26C 109.5

C26—P3—C28 106.8 (5) P4—C27—H27A 109.5

C5—P3—C28 103.8 (4) P4—C27—H27B 109.5


S24

C26—P3—Pt1 117.3 (3) H27A—C27—H27B 109.5

C5—P3—Pt1 107.3 (3) P4—C27—H27C 109.5

C28—P3—Pt1 116.2 (3) H27A—C27—H27C 109.5

C27—P4—C14 104.7 (5) H27B—C27—H27C 109.5

C27—P4—C32 107.5 (5) C31—C28—C30 108.4 (8)

C14—P4—C32 105.2 (4) C31—C28—C29 111.7 (7)

C27—P4—Pt1 118.5 (4) C30—C28—C29 109.0 (8)

C14—P4—Pt1 107.0 (3) C31—C28—P3 111.1 (6)

C32—P4—Pt1 112.8 (3) C30—C28—P3 109.5 (6)

N6—C5—C14 122.2 (9) C29—C28—P3 107.0 (6)

N6—C5—P3 118.6 (7) C28—C29—H29A 109.5

C14—C5—P3 119.1 (7) C28—C29—H29B 109.5

C5—N6—C7 114.8 (7) H29A—C29—H29B 109.5

N6—C7—C12 123.9 (8) C28—C29—H29C 109.5

N6—C7—C8 119.0 (8) H29A—C29—H29C 109.5

C12—C7—C8 117.0 (8) H29B—C29—H29C 109.5

C9—C8—C7 119.9 (9) C28—C30—H30A 109.5

C9—C8—H8 120.0 C28—C30—H30B 109.5

C7—C8—H8 120.0 H30A—C30—H30B 109.5

C8—C9—C10 120.7 (9) C28—C30—H30C 109.5

C8—C9—H9 119.6 H30A—C30—H30C 109.5

C10—C9—H9 119.6 H30B—C30—H30C 109.5

C11—C10—C9 121.7 (9) C28—C31—H31A 109.5

C11—C10—H10 119.2 C28—C31—H31B 109.5

C9—C10—H10 119.2 H31A—C31—H31B 109.5

C10—C11—C12 118.8 (9) C28—C31—H31C 109.5

C10—C11—H11 120.6 H31A—C31—H31C 109.5

C12—C11—H11 120.6 H31B—C31—H31C 109.5


S25

N13—C12—C11 119.2 (8) C34—C32—C33 109.9 (8)

N13—C12—C7 119.0 (8) C34—C32—C35 108.5 (8)

C11—C12—C7 121.7 (8) C33—C32—C35 108.7 (8)

C14—N13—C12 116.1 (7) C34—C32—P4 108.7 (6)

N13—C14—C5 123.2 (8) C33—C32—P4 111.6 (6)

N13—C14—P4 120.5 (6) C35—C32—P4 109.4 (7)

C5—C14—P4 116.2 (7) C32—C33—H33A 109.5

C16—C15—C20 115.7 (9) C32—C33—H33B 109.5

C16—C15—Pt1 120.4 (6) H33A—C33—H33B 109.5

C20—C15—Pt1 123.2 (6) C32—C33—H33C 109.5

C15—C16—F25 120.9 (9) H33A—C33—H33C 109.5

C15—C16—C17 124.7 (9) H33B—C33—H33C 109.5

F25—C16—C17 114.5 (9) C32—C34—H34A 109.5

F24—C17—C18 121.2 (8) C32—C34—H34B 109.5

F24—C17—C16 121.4 (9) H34A—C34—H34B 109.5

C18—C17—C16 117.4 (9) C32—C34—H34C 109.5

F23—C18—C19 119.7 (8) H34A—C34—H34C 109.5

F23—C18—C17 120.3 (9) H34B—C34—H34C 109.5

C19—C18—C17 119.9 (8) C32—C35—H35A 109.5

C18—C19—F22 120.5 (8) C32—C35—H35B 109.5

C18—C19—C20 120.7 (8) H35A—C35—H35B 109.5

F22—C19—C20 118.7 (8) C32—C35—H35C 109.5

F21—C20—C15 120.9 (8) H35A—C35—H35C 109.5

F21—C20—C19 117.6 (7) H35B—C35—H35C 109.5 All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.


S26

Complex 1 Crystal data

C30H32F6N2P2Pt ?

Mr = 791.61 Dx = 1.739 Mg m−3

Orthorhombic, P212121 Melting point: ? K



b = 15.6326 (5) Å θ = 1.4–27.9°

c = 24.5087 (9) Å µ = 4.81 mm−1

V = 3024.24 (17) Å3 T = 110 K

Z = 4 Prism, yellow

F(000) = 1552 0.30 × 0.20 × 0.20 mm

Data collection





1 deg. φ scan h = −9 8


Tmin = 0.327, Tmax = 0.447 l = −32 32


Refinement




S27

R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.0747P)2 + 0.6035P]


2)/3

wR(F2) = 0.123 (Δ/σ)max < 0.001

S = 1.06 Δρmax = 2.06 e Å−3



0 restraints Extinction coefficient: ?




Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R– factors based on ALL data will be even larger.


x y z Uiso*/Ueq

Pt1 −0.12626 (4) −0.141312 (19) −0.170136 (12) 0.03957 (11)

P2 −0.2395 (3) −0.01698 (15) −0.20260 (9) 0.0458 (6)

P3 −0.1747 (3) −0.08999 (13) −0.08442 (9) 0.0398 (5)

C4 −0.2944 (11) 0.0095 (5) −0.0905 (4) 0.042 (2)

N5 −0.3730 (11) 0.0430 (4) −0.0485 (3) 0.0421 (14)

C6 −0.4480 (11) 0.1203 (5) −0.0552 (4) 0.044 (2)

C7 −0.5392 (12) 0.1570 (6) −0.0123 (5) 0.061 (3)

H7 −0.5515 0.1279 0.0215 0.074*

C8 −0.6111 (16) 0.2366 (7) −0.0202 (5) 0.072 (3)

H8 −0.6766 0.2618 0.0081 0.086*

C9 −0.5884 (17) 0.2811 (7) −0.0698 (6) 0.083 (5)


S28

H9 −0.6348 0.3369 −0.0732 0.099*

C10 −0.5047 (16) 0.2480 (6) −0.1122 (5) 0.068 (3)

H10 −0.4917 0.2792 −0.1452 0.081*

C11 −0.4346 (13) 0.1637 (6) −0.1063 (4) 0.053 (2)

N12 −0.3622 (11) 0.1268 (4) −0.1508 (3) 0.0482 (17)

C13 −0.2997 (11) 0.0480 (5) −0.1434 (4) 0.0404 (19)

C14 −0.0460 (12) −0.2603 (6) −0.1421 (3) 0.045 (2)

C15 −0.1571 (12) −0.3240 (6) −0.1286 (4) 0.047 (2)

C16 −0.1118 (17) −0.4048 (7) −0.1125 (4) 0.061 (3)

C17 0.0558 (19) −0.4251 (8) −0.1099 (4) 0.071 (3)

C18 0.1697 (12) −0.3646 (7) −0.1204 (4) 0.057 (3)

C19 0.1226 (15) −0.2845 (6) −0.1374 (4) 0.052 (2)

F20 −0.3293 (10) −0.3102 (5) −0.1333 (4) 0.093 (2)

F21 −0.2400 (13) −0.4696 (5) −0.1043 (4) 0.107 (3)

F22 0.1049 (12) −0.5056 (4) −0.0941 (3) 0.087 (2)

F23 0.3338 (12) −0.3891 (5) −0.1150 (3) 0.098 (3)

F24 0.2445 (9) −0.2315 (5) −0.1458 (3) 0.085 (2)

C25 −0.0769 (11) −0.1887 (6) −0.2481 (4) 0.047 (2)

C26 0.0360 (11) −0.1476 (8) −0.2832 (4) 0.060 (3)

H26 0.0907 −0.0964 −0.2718 0.071*

C27 0.0703 (13) −0.1827 (8) −0.3370 (4) 0.065 (3)

H27 0.1500 −0.1566 −0.3608 0.078*

C28 −0.0169 (14) −0.2550 (8) −0.3521 (4) 0.062 (3)

C29 −0.1358 (14) −0.2926 (6) −0.3195 (4) 0.055 (2)

H29 −0.1993 −0.3402 −0.3323 0.066*

C30 −0.1625 (12) −0.2598 (6) −0.2671 (4) 0.051 (2)

H30 −0.2419 −0.2873 −0.2439 0.061*

F31 0.0147 (10) −0.2880 (5) −0.4019 (3) 0.087 (2)


S29

C32 −0.2997 (15) −0.1513 (7) −0.0381 (4) 0.061 (3)

H32A −0.3371 −0.1147 −0.0079 0.092*

H32B −0.2319 −0.1986 −0.0236 0.092*

H32C −0.3989 −0.1742 −0.0572 0.092*

C33 0.0185 (12) −0.0562 (6) −0.0455 (4) 0.046 (2)

C34 −0.0190 (16) 0.0063 (7) 0.0012 (4) 0.067 (3)

H34A 0.0845 0.0160 0.0224 0.101*

H34B −0.1067 −0.0178 0.0249 0.101*

H34C −0.0587 0.0608 −0.0140 0.101*

C35 0.1043 (19) −0.1349 (7) −0.0225 (6) 0.092 (5)

H35A 0.1647 −0.1648 −0.0518 0.138*

H35B 0.0189 −0.1730 −0.0067 0.138*

H35C 0.1850 −0.1178 0.0058 0.138*

C36 0.132 (2) −0.0151 (9) −0.0859 (5) 0.084 (4)

H36A 0.2409 −0.0018 −0.0686 0.125*

H36B 0.0798 0.0378 −0.0992 0.125*

H36C 0.1507 −0.0542 −0.1166 0.125*

C37 −0.1211 (17) 0.0550 (7) −0.2432 (4) 0.069 (3)

H37A −0.1740 0.1117 −0.2420 0.103*

H37B −0.1185 0.0344 −0.2810 0.103*

H37C −0.0051 0.0587 −0.2291 0.103*

C38 −0.4442 (16) −0.0338 (8) −0.2386 (5) 0.070 (3)

C39 −0.405 (2) −0.0714 (8) −0.2916 (6) 0.099 (5)

H39A −0.5109 −0.0876 −0.3100 0.148*

H39B −0.3346 −0.1223 −0.2865 0.148*

H39C −0.3444 −0.0295 −0.3140 0.148*

C40 −0.534 (2) 0.0488 (10) −0.2522 (7) 0.105 (6)

H40A −0.4556 0.0876 −0.2708 0.157*


S30

H40B −0.5747 0.0756 −0.2185 0.157*

H40C −0.6308 0.0367 −0.2761 0.157*

C41 −0.5574 (19) −0.0861 (13) −0.2001 (8) 0.142 (9)

H41A −0.5550 −0.0606 −0.1636 0.214*

H41B −0.5156 −0.1451 −0.1982 0.214*

H41C −0.6740 −0.0861 −0.2139 0.214*


U11 U22 U33 U12 U13 U23

Pt1 0.04554 (18) 0.03956 (16) 0.03362 (15) −0.00542 (15) 0.00169 (15) −0.00582 (13)

P2 0.0600 (15) 0.0463 (13) 0.0311 (12) −0.0101 (11) −0.0021 (10) 0.0015 (10)

P3 0.0551 (14) 0.0331 (11) 0.0313 (10) −0.0002 (9) 0.0000 (9) 0.0006 (8)

C4 0.050 (5) 0.034 (4) 0.042 (5) 0.000 (4) −0.010 (4) 0.002 (4)

N5 0.050 (4) 0.041 (3) 0.035 (3) −0.008 (4) −0.003 (4) −0.001 (3)

C6 0.038 (4) 0.044 (5) 0.051 (5) 0.000 (3) −0.004 (4) −0.016 (4)

C7 0.048 (5) 0.057 (6) 0.079 (7) 0.003 (4) −0.011 (5) −0.022 (5)

C8 0.070 (7) 0.071 (7) 0.075 (8) 0.016 (6) −0.028 (7) −0.033 (6)

C9 0.099 (10) 0.046 (6) 0.104 (10) 0.030 (6) −0.062 (8) −0.031 (6)

C10 0.094 (8) 0.034 (5) 0.075 (8) 0.013 (5) −0.041 (7) −0.004 (5)

C11 0.064 (6) 0.038 (5) 0.055 (6) 0.001 (4) −0.020 (5) −0.013 (4)

N12 0.066 (5) 0.036 (4) 0.043 (4) −0.005 (4) −0.008 (4) 0.004 (3)

C13 0.053 (5) 0.030 (4) 0.038 (5) −0.001 (3) −0.010 (4) 0.003 (3)

C14 0.062 (5) 0.045 (5) 0.028 (4) 0.000 (4) −0.002 (4) −0.011 (4)

C15 0.057 (7) 0.040 (4) 0.044 (5) 0.002 (4) 0.006 (4) 0.003 (4)

C16 0.076 (7) 0.063 (6) 0.043 (5) 0.001 (6) 0.007 (6) 0.002 (4)

C17 0.117 (11) 0.058 (7) 0.039 (6) 0.017 (7) 0.002 (6) 0.000 (5)

C18 0.059 (6) 0.063 (6) 0.048 (5) 0.022 (5) −0.012 (4) −0.014 (5)

C19 0.056 (5) 0.056 (5) 0.045 (5) −0.001 (6) −0.002 (5) −0.012 (4)


S31

F20 0.094 (6) 0.079 (5) 0.107 (6) −0.007 (4) 0.021 (4) −0.001 (4)

F21 0.144 (7) 0.075 (5) 0.101 (6) −0.033 (5) 0.027 (6) 0.005 (5)

F22 0.147 (7) 0.059 (4) 0.055 (4) 0.036 (5) 0.005 (4) 0.012 (3)

F23 0.122 (7) 0.089 (5) 0.082 (5) 0.018 (5) −0.022 (5) 0.001 (4)

F24 0.080 (5) 0.074 (4) 0.099 (6) 0.000 (4) 0.005 (4) 0.008 (4)

C25 0.054 (6) 0.048 (5) 0.038 (5) 0.001 (4) 0.002 (4) −0.004 (4)

C26 0.035 (5) 0.085 (7) 0.059 (6) 0.001 (5) −0.004 (4) −0.015 (6)

C27 0.056 (6) 0.091 (8) 0.047 (6) 0.032 (5) 0.001 (5) 0.006 (6)

C28 0.065 (7) 0.083 (8) 0.037 (5) 0.035 (6) 0.007 (5) −0.007 (5)

C29 0.062 (6) 0.056 (5) 0.047 (5) 0.010 (5) −0.008 (5) −0.015 (4)

C30 0.057 (6) 0.053 (5) 0.041 (5) 0.000 (4) −0.003 (4) −0.018 (4)

F31 0.111 (5) 0.104 (6) 0.045 (4) 0.042 (5) 0.000 (4) −0.022 (4)

C32 0.093 (7) 0.040 (5) 0.051 (6) −0.003 (5) 0.007 (5) 0.005 (5)

C33 0.062 (6) 0.041 (5) 0.037 (5) 0.004 (4) −0.016 (4) −0.013 (4)

C34 0.092 (8) 0.066 (7) 0.043 (6) 0.001 (6) −0.019 (6) −0.018 (5)

C35 0.127 (11) 0.056 (6) 0.094 (9) 0.030 (8) −0.066 (9) −0.020 (6)

C36 0.081 (8) 0.102 (9) 0.068 (7) −0.026 (9) 0.001 (8) −0.019 (7)

C37 0.075 (7) 0.083 (7) 0.050 (6) −0.017 (7) 0.012 (6) 0.016 (5)

C38 0.074 (8) 0.074 (8) 0.064 (7) −0.002 (6) −0.013 (6) 0.005 (6)

C39 0.136 (13) 0.072 (8) 0.089 (10) 0.020 (9) −0.033 (9) −0.032 (7)

C40 0.111 (12) 0.094 (11) 0.109 (12) 0.025 (9) −0.064 (10) −0.001 (9)

C41 0.077 (9) 0.21 (2) 0.143 (15) −0.083 (11) −0.053 (10) 0.083 (15)


Pt1—C14 2.082 (9) C26—H26 0.9500

Pt1—C25 2.086 (9) C27—C28 1.374 (17)

Pt1—P3 2.281 (2) C27—H27 0.9500

Pt1—P2 2.282 (3) C28—F31 1.350 (11)


S32

P2—C37 1.769 (10) C28—C29 1.365 (16)

P2—C13 1.835 (9) C29—C30 1.399 (12)

P2—C38 1.860 (12) C29—H29 0.9500

P3—C32 1.784 (10) C30—H30 0.9500

P3—C4 1.825 (9) C32—H32A 0.9800

P3—C33 1.874 (9) C32—H32B 0.9800

C4—N5 1.312 (11) C32—H32C 0.9800

C4—C13 1.429 (12) C33—C36 1.483 (16)

N5—C6 1.355 (11) C33—C35 1.513 (14)

C6—C7 1.398 (14) C33—C34 1.534 (13)

C6—C11 1.428 (14) C34—H34A 0.9800

C7—C8 1.381 (14) C34—H34B 0.9800

C7—H7 0.9500 C34—H34C 0.9800

C8—C9 1.413 (19) C35—H35A 0.9800

C8—H8 0.9500 C35—H35B 0.9800

C9—C10 1.335 (18) C35—H35C 0.9800

C9—H9 0.9500 C36—H36A 0.9800

C10—C11 1.437 (13) C36—H36B 0.9800

C10—H10 0.9500 C36—H36C 0.9800

C11—N12 1.361 (13) C37—H37A 0.9800

N12—C13 1.340 (10) C37—H37B 0.9800

C14—C15 1.367 (13) C37—H37C 0.9800

C14—C19 1.388 (15) C38—C39 1.458 (18)

C15—C16 1.372 (14) C38—C40 1.511 (18)

C15—F20 1.381 (12) C38—C41 1.536 (19)

C16—C17 1.362 (18) C39—H39A 0.9800

C16—F21 1.445 (15) C39—H39B 0.9800

C17—C18 1.330 (16) C39—H39C 0.9800


S33

C17—F22 1.373 (13) C40—H40A 0.9800

C18—F23 1.357 (12) C40—H40B 0.9800

C18—C19 1.372 (14) C40—H40C 0.9800

C19—F24 1.287 (12) C41—H41A 0.9800

C25—C30 1.382 (13) C41—H41B 0.9800

C25—C26 1.395 (14) C41—H41C 0.9800

C26—C27 1.454 (14)

C14—Pt1—C25 85.9 (3) C26—C27—H27 121.3

C14—Pt1—P3 93.5 (2) F31—C28—C29 119.4 (11)

C25—Pt1—P3 178.9 (3) F31—C28—C27 117.8 (11)

C14—Pt1—P2 174.3 (3) C29—C28—C27 122.8 (9)

C25—Pt1—P2 93.2 (3) C28—C29—C30 118.9 (10)

P3—Pt1—P2 87.47 (8) C28—C29—H29 120.6

C37—P2—C13 103.3 (5) C30—C29—H29 120.6

C37—P2—C38 106.4 (6) C25—C30—C29 122.0 (10)

C13—P2—C38 103.2 (5) C25—C30—H30 119.0

C37—P2—Pt1 122.1 (5) C29—C30—H30 119.0

C13—P2—Pt1 107.3 (3) P3—C32—H32A 109.5

C38—P2—Pt1 112.6 (4) P3—C32—H32B 109.5

C32—P3—C4 102.9 (5) H32A—C32—H32B 109.5

C32—P3—C33 106.1 (5) P3—C32—H32C 109.5

C4—P3—C33 102.9 (4) H32A—C32—H32C 109.5

C32—P3—Pt1 119.4 (4) H32B—C32—H32C 109.5

C4—P3—Pt1 108.1 (3) C36—C33—C35 109.3 (11)

C33—P3—Pt1 115.5 (3) C36—C33—C34 109.8 (9)

N5—C4—C13 121.9 (8) C35—C33—C34 109.1 (9)

N5—C4—P3 121.4 (7) C36—C33—P3 105.9 (7)

C13—C4—P3 116.7 (7) C35—C33—P3 109.0 (7)


S34

C4—N5—C6 117.9 (7) C34—C33—P3 113.7 (7)

N5—C6—C7 120.0 (9) C33—C34—H34A 109.5

N5—C6—C11 119.8 (8) C33—C34—H34B 109.5

C7—C6—C11 120.1 (9) H34A—C34—H34B 109.5

C8—C7—C6 118.5 (11) C33—C34—H34C 109.5

C8—C7—H7 120.8 H34A—C34—H34C 109.5

C6—C7—H7 120.8 H34B—C34—H34C 109.5

C7—C8—C9 120.8 (11) C33—C35—H35A 109.5

C7—C8—H8 119.6 C33—C35—H35B 109.5

C9—C8—H8 119.6 H35A—C35—H35B 109.5

C10—C9—C8 122.8 (10) C33—C35—H35C 109.5

C10—C9—H9 118.6 H35A—C35—H35C 109.5

C8—C9—H9 118.6 H35B—C35—H35C 109.5

C9—C10—C11 117.9 (12) C33—C36—H36A 109.5

C9—C10—H10 121.1 C33—C36—H36B 109.5

C11—C10—H10 121.1 H36A—C36—H36B 109.5

N12—C11—C6 122.3 (8) C33—C36—H36C 109.5

N12—C11—C10 117.9 (10) H36A—C36—H36C 109.5

C6—C11—C10 119.7 (10) H36B—C36—H36C 109.5

C13—N12—C11 115.7 (8) P2—C37—H37A 109.5

N12—C13—C4 121.5 (8) P2—C37—H37B 109.5

N12—C13—P2 119.8 (6) H37A—C37—H37B 109.5

C4—C13—P2 118.4 (6) P2—C37—H37C 109.5

C15—C14—C19 113.4 (9) H37A—C37—H37C 109.5

C15—C14—Pt1 122.3 (7) H37B—C37—H37C 109.5

C19—C14—Pt1 124.3 (7) C39—C38—C40 104.3 (11)

C14—C15—C16 125.0 (10) C39—C38—C41 117.1 (13)

C14—C15—F20 119.9 (8) C40—C38—C41 108.5 (13)


S35

C16—C15—F20 115.1 (9) C39—C38—P2 107.3 (10)

C17—C16—C15 118.7 (11) C40—C38—P2 113.1 (9)

C17—C16—F21 120.7 (11) C41—C38—P2 106.8 (8)

C15—C16—F21 120.2 (11) C38—C39—H39A 109.5

C18—C17—C16 118.8 (11) C38—C39—H39B 109.5

C18—C17—F22 121.0 (12) H39A—C39—H39B 109.5

C16—C17—F22 120.0 (12) C38—C39—H39C 109.5

C17—C18—F23 115.2 (11) H39A—C39—H39C 109.5

C17—C18—C19 121.6 (10) H39B—C39—H39C 109.5

F23—C18—C19 123.1 (11) C38—C40—H40A 109.5

F24—C19—C18 115.7 (10) C38—C40—H40B 109.5

F24—C19—C14 121.9 (9) H40A—C40—H40B 109.5

C18—C19—C14 122.3 (10) C38—C40—H40C 109.5

C30—C25—C26 118.4 (9) H40A—C40—H40C 109.5

C30—C25—Pt1 120.2 (7) H40B—C40—H40C 109.5

C26—C25—Pt1 121.3 (7) C38—C41—H41A 109.5

C25—C26—C27 120.3 (11) C38—C41—H41B 109.5

C25—C26—H26 119.9 H41A—C41—H41B 109.5

C27—C26—H26 119.9 C38—C41—H41C 109.5

C28—C27—C26 117.5 (11) H41A—C41—H41C 109.5

C28—C27—H27 121.3 H41B—C41—H41C 109.5 All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.


S36

Complex 2

Crystal data

C30H32Br2F6N2P2Pt ?

Mr = 951.43 Dx = 1.611 Mg m−3

Orthorhombic, P212121 Melting point: ? K



b = 12.3660 (3) Å θ = 2.6–27.7°

c = 30.6670 (7) Å µ = 5.75 mm−1

V = 3921.75 (15) Å3 T = 110 K

Z = 4 Rods, yellow

F(000) = 1832 0.30 × 0.15 × 0.15 mm

Data collection





1 deg. ω scans h = −13 13


Tmin = 0.278, Tmax = 0.479 l = −39 40


Refinement



S37


R[F2 > 2σ(F2)] = 0.053 w = 1/[σ2(Fo2) + (0.0789P)2 + 7.5669P]


2)/3

wR(F2) = 0.152 (Δ/σ)max < 0.001

S = 1.04 Δρmax = 1.76 e Å−3



0 restraints Extinction coefficient: ?




Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R– factors based on ALL data will be even larger.

The lattice contains also severely disordered pentane solvent, as indicated by several residual electron-density peaks (within 1.0–1.7 e/A**3) present in areas between molecules of the Pt-compound. The pentane solvent could not be modeled by discrete atoms, and was therefore excluded from the structural model.


x y z Uiso*/Ueq

Pt1 0.16605 (4) 0.00723 (3) 0.132558 (13) 0.02887 (12)

Br2 0.24344 (12) 0.06737 (10) 0.20519 (4) 0.0420 (3)

Br3 0.08479 (12) −0.05790 (10) 0.06123 (4) 0.0386 (3)

P4 −0.0524 (3) −0.0123 (3) 0.16352 (9) 0.0319 (6)

P5 0.1089 (3) 0.1922 (2) 0.11961 (10) 0.0329 (7)

C6 −0.1117 (12) 0.1268 (11) 0.1676 (4) 0.039 (3)

N7 −0.2281 (10) 0.1401 (8) 0.1864 (3) 0.038 (2)


S38

C8 −0.2707 (13) 0.2448 (11) 0.1895 (4) 0.047 (3)

C9 −0.3947 (13) 0.2617 (11) 0.2106 (4) 0.047 (3)

H9 −0.4450 0.2031 0.2212 0.057*

C10 −0.4339 (14) 0.3629 (14) 0.2142 (5) 0.063 (4)

H10 −0.5160 0.3758 0.2271 0.075*

C11 −0.3593 (15) 0.4556 (14) 0.1998 (5) 0.065 (4)

H11 −0.3898 0.5268 0.2051 0.079*

C12 −0.2471 (14) 0.4399 (11) 0.1789 (4) 0.055 (4)

H12 −0.2000 0.4998 0.1678 0.066*

C13 −0.1980 (12) 0.3306 (9) 0.1734 (4) 0.037 (3)

N14 −0.0818 (10) 0.3169 (8) 0.1540 (3) 0.036 (2)

C15 −0.0395 (12) 0.2155 (10) 0.1490 (4) 0.038 (3)

C16 0.2313 (12) −0.1501 (9) 0.1480 (4) 0.035 (3)

C17 0.3529 (11) −0.1734 (10) 0.1637 (4) 0.038 (3)

C18 0.3940 (12) −0.2752 (11) 0.1724 (4) 0.042 (3)

C19 0.3142 (13) −0.3621 (10) 0.1668 (5) 0.049 (3)

C20 0.1977 (13) −0.3452 (9) 0.1497 (4) 0.043 (3)

C21 0.1554 (11) −0.2401 (8) 0.1412 (4) 0.036 (3)

F22 0.4410 (6) −0.0944 (6) 0.1716 (2) 0.0447 (18)

F23 0.5181 (7) −0.2926 (6) 0.1885 (3) 0.054 (2)

F24 0.3577 (7) −0.4652 (5) 0.1749 (3) 0.061 (2)

F25 0.1149 (7) −0.4295 (5) 0.1404 (3) 0.055 (2)

F26 0.0323 (6) −0.2337 (5) 0.1272 (3) 0.0459 (18)

C27 0.3493 (10) 0.0297 (9) 0.1034 (3) 0.033 (3)

C28 0.4328 (12) 0.1102 (11) 0.1156 (4) 0.044 (3)

H28 0.4105 0.1564 0.1392 0.053*

C29 0.5529 (11) 0.1257 (11) 0.0935 (5) 0.049 (4)

H29 0.6078 0.1842 0.1012 0.059*


S39

C30 0.5866 (11) 0.0589 (12) 0.0626 (4) 0.041 (3)

C31 0.5068 (13) −0.0248 (12) 0.0503 (4) 0.055 (4)

H31 0.5337 −0.0724 0.0278 0.065*

C32 0.3897 (11) −0.0406 (11) 0.0699 (4) 0.045 (3)

H32 0.3357 −0.0987 0.0610 0.054*

F33 0.7011 (6) 0.0709 (7) 0.0423 (3) 0.065 (2)

C34 −0.1771 (10) −0.0675 (10) 0.1284 (4) 0.042 (3)

H34A −0.2623 −0.0519 0.1409 0.063*

H34B −0.1657 −0.1460 0.1260 0.063*

H34C −0.1706 −0.0346 0.0994 0.063*

C35 −0.0882 (12) −0.0701 (10) 0.2194 (4) 0.044 (3)

C36 −0.2245 (12) −0.1117 (12) 0.2222 (4) 0.050 (3)

H36A −0.2423 −0.1583 0.1971 0.075*

H36B −0.2848 −0.0506 0.2222 0.075*

H36C −0.2352 −0.1533 0.2492 0.075*

C37 −0.0646 (13) 0.0148 (11) 0.2563 (4) 0.048 (3)

H37A −0.1274 0.0737 0.2535 0.073*

H37B 0.0232 0.0439 0.2537 0.073*

H37C −0.0748 −0.0201 0.2848 0.073*

C38 0.0043 (13) −0.1697 (10) 0.2248 (4) 0.043 (3)

H38A 0.0041 −0.1934 0.2553 0.065*

H38B 0.0922 −0.1491 0.2163 0.065*

H38C −0.0257 −0.2290 0.2062 0.065*

C39 0.2131 (12) 0.2935 (9) 0.1434 (4) 0.036 (3)

H39A 0.1655 0.3617 0.1462 0.054*

H39B 0.2885 0.3044 0.1245 0.054*

H39C 0.2417 0.2694 0.1722 0.054*

C40 0.0750 (13) 0.2468 (10) 0.0627 (4) 0.042 (3)


S40

C41 −0.0522 (12) 0.2019 (11) 0.0468 (4) 0.046 (3)

H41A −0.0627 0.2185 0.0157 0.069*

H41B −0.1232 0.2348 0.0633 0.069*

H41C −0.0534 0.1234 0.0510 0.069*

C42 0.1903 (13) 0.2153 (10) 0.0332 (4) 0.045 (3)

H42A 0.2089 0.1381 0.0367 0.067*

H42B 0.2666 0.2576 0.0416 0.067*

H42C 0.1687 0.2303 0.0027 0.067*

C43 0.0686 (15) 0.3736 (11) 0.0640 (4) 0.055 (4)

H43A 0.1536 0.4026 0.0719 0.082*

H43B 0.0044 0.3965 0.0856 0.082*

H43C 0.0438 0.4010 0.0352 0.082*


U11 U22 U33 U12 U13 U23

Pt1 0.02869 (19) 0.0238 (2) 0.0341 (2) 0.00277 (19) 0.00095 (18) 0.0035 (2)

Br2 0.0457 (7) 0.0411 (7) 0.0392 (6) −0.0003 (6) −0.0049 (6) 0.0026 (6)

Br3 0.0413 (6) 0.0347 (6) 0.0398 (7) 0.0002 (5) −0.0011 (6) 0.0002 (6)

P4 0.0281 (13) 0.0307 (16) 0.0371 (14) 0.0050 (13) 0.0016 (11) 0.0050 (15)

P5 0.0346 (16) 0.0268 (15) 0.0373 (17) 0.0007 (12) −0.0012 (13) 0.0034 (13)

C6 0.034 (7) 0.047 (8) 0.036 (7) 0.010 (6) −0.001 (5) 0.008 (6)

N7 0.041 (6) 0.036 (6) 0.037 (5) 0.008 (5) 0.003 (5) 0.004 (4)

C8 0.039 (7) 0.062 (9) 0.039 (7) 0.026 (7) −0.003 (6) −0.001 (6)

C9 0.038 (7) 0.058 (9) 0.046 (8) 0.018 (6) 0.009 (6) 0.000 (7)

C10 0.047 (9) 0.089 (13) 0.052 (9) 0.037 (9) 0.009 (7) −0.008 (8)

C11 0.068 (10) 0.068 (10) 0.060 (9) 0.043 (8) −0.010 (8) −0.013 (8)

C12 0.052 (8) 0.050 (8) 0.062 (9) 0.030 (7) −0.005 (7) −0.002 (7)

C13 0.049 (8) 0.032 (6) 0.029 (6) 0.015 (5) −0.021 (5) −0.002 (5)


S41

N14 0.043 (6) 0.029 (5) 0.037 (6) 0.009 (5) 0.000 (5) −0.006 (4)

C15 0.038 (7) 0.037 (7) 0.038 (7) 0.005 (5) −0.009 (5) 0.006 (5)

C16 0.039 (7) 0.021 (6) 0.043 (7) 0.003 (5) 0.005 (6) 0.006 (5)

C17 0.033 (7) 0.036 (6) 0.046 (7) 0.010 (6) 0.011 (6) 0.009 (6)

C18 0.030 (7) 0.043 (8) 0.053 (8) 0.006 (6) −0.003 (6) 0.006 (6)

C19 0.045 (8) 0.039 (7) 0.065 (9) 0.014 (6) 0.001 (7) 0.012 (7)

C20 0.049 (8) 0.024 (6) 0.057 (8) −0.004 (5) −0.001 (6) 0.007 (6)

C21 0.035 (6) 0.023 (5) 0.050 (7) 0.008 (5) −0.007 (6) 0.005 (5)

F22 0.038 (4) 0.039 (4) 0.057 (4) −0.008 (3) −0.013 (3) 0.017 (4)

F23 0.053 (5) 0.038 (4) 0.072 (5) 0.010 (4) −0.009 (4) 0.007 (4)

F24 0.055 (5) 0.031 (4) 0.096 (6) 0.013 (3) −0.003 (4) 0.018 (4)

F25 0.057 (4) 0.021 (3) 0.086 (6) 0.000 (3) 0.001 (4) 0.008 (4)

F26 0.036 (4) 0.030 (3) 0.071 (5) 0.000 (3) −0.006 (4) 0.001 (4)

C27 0.028 (6) 0.044 (7) 0.027 (5) 0.010 (5) 0.003 (5) 0.016 (5)

C28 0.037 (7) 0.046 (8) 0.049 (8) 0.009 (6) −0.014 (6) 0.004 (6)

C29 0.026 (6) 0.048 (8) 0.073 (10) −0.011 (6) −0.008 (7) 0.024 (8)

C30 0.023 (6) 0.059 (8) 0.041 (7) 0.005 (6) 0.007 (6) 0.022 (7)

C31 0.044 (7) 0.064 (11) 0.056 (8) 0.012 (7) 0.020 (6) 0.009 (7)

C32 0.036 (6) 0.057 (8) 0.042 (7) 0.012 (6) 0.012 (6) 0.017 (6)

F33 0.031 (4) 0.090 (6) 0.076 (5) −0.006 (4) 0.011 (4) 0.041 (5)

C34 0.027 (6) 0.048 (7) 0.050 (7) −0.006 (5) −0.005 (6) 0.001 (6)

C35 0.040 (7) 0.039 (7) 0.054 (8) 0.001 (6) −0.001 (6) 0.022 (6)

C36 0.040 (7) 0.058 (9) 0.052 (8) −0.008 (6) 0.001 (6) 0.012 (7)

C37 0.057 (7) 0.053 (8) 0.035 (6) 0.011 (7) 0.010 (6) 0.013 (7)

C38 0.042 (7) 0.036 (7) 0.052 (8) 0.001 (6) 0.005 (6) 0.016 (6)

C39 0.044 (7) 0.033 (6) 0.031 (6) 0.008 (5) −0.005 (5) −0.002 (5)

C40 0.048 (7) 0.030 (7) 0.049 (7) −0.009 (6) 0.011 (7) 0.005 (6)

C41 0.040 (8) 0.056 (9) 0.042 (7) 0.013 (6) −0.004 (6) 0.003 (6)


S42

C42 0.051 (8) 0.045 (7) 0.038 (7) 0.006 (6) 0.009 (6) 0.017 (6)

C43 0.067 (9) 0.054 (9) 0.043 (8) 0.006 (7) −0.002 (7) 0.021 (7)


Pt1—C27 2.113 (10) C28—C29 1.428 (18)

Pt1—C16 2.113 (11) C28—H28 0.9500

Pt1—P5 2.396 (3) C29—C30 1.304 (19)

Pt1—P4 2.462 (3) C29—H29 0.9500

Pt1—Br3 2.4777 (13) C30—F33 1.346 (13)

Pt1—Br2 2.4809 (12) C30—C31 1.376 (19)

P4—C34 1.813 (11) C31—C32 1.366 (17)

P4—C6 1.830 (13) C31—H31 0.9500

P4—C35 1.894 (12) C32—H32 0.9500

P5—C15 1.803 (13) C34—H34A 0.9800

P5—C39 1.805 (12) C34—H34B 0.9800

P5—C40 1.905 (13) C34—H34C 0.9800

C6—N7 1.345 (15) C35—C36 1.503 (17)

C6—C15 1.444 (17) C35—C37 1.562 (18)

N7—C8 1.371 (15) C35—C38 1.568 (17)

C8—C13 1.391 (18) C36—H36A 0.9800

C8—C9 1.452 (17) C36—H36B 0.9800

C9—C10 1.320 (19) C36—H36C 0.9800

C9—H9 0.9500 C37—H37A 0.9800

C10—C11 1.45 (2) C37—H37B 0.9800

C10—H10 0.9500 C37—H37C 0.9800

C11—C12 1.34 (2) C38—H38A 0.9800

C11—H11 0.9500 C38—H38B 0.9800

C12—C13 1.454 (16) C38—H38C 0.9800


S43

C12—H12 0.9500 C39—H39A 0.9800

C13—N14 1.351 (15) C39—H39B 0.9800

N14—C15 1.337 (15) C39—H39C 0.9800

C16—C17 1.377 (17) C40—C41 1.508 (18)

C16—C21 1.378 (16) C40—C42 1.546 (18)

C17—C18 1.355 (17) C40—C43 1.570 (17)

C17—F22 1.358 (14) C41—H41A 0.9800

C18—C19 1.366 (18) C41—H41B 0.9800

C18—F23 1.392 (14) C41—H41C 0.9800

C19—C20 1.329 (18) C42—H42A 0.9800

C19—F24 1.375 (14) C42—H42B 0.9800

C20—F25 1.379 (14) C42—H42C 0.9800

C20—C21 1.396 (15) C43—H43A 0.9800

C21—F26 1.346 (13) C43—H43B 0.9800

C27—C28 1.370 (17) C43—H43C 0.9800

C27—C32 1.410 (17)

C27—Pt1—C16 85.9 (4) C27—C28—H28 119.5

C27—Pt1—P5 91.5 (3) C29—C28—H28 119.5

C16—Pt1—P5 174.3 (3) C30—C29—C28 119.5 (13)

C27—Pt1—P4 176.9 (3) C30—C29—H29 120.3

C16—Pt1—P4 96.7 (3) C28—C29—H29 120.3

P5—Pt1—P4 86.06 (11) C29—C30—F33 120.1 (13)

C27—Pt1—Br3 88.5 (3) C29—C30—C31 121.0 (11)

C16—Pt1—Br3 90.4 (3) F33—C30—C31 118.9 (13)

P5—Pt1—Br3 94.61 (8) C32—C31—C30 121.2 (13)

P4—Pt1—Br3 89.85 (8) C32—C31—H31 119.4

C27—Pt1—Br2 92.9 (3) C30—C31—H31 119.4

C16—Pt1—Br2 88.4 (3) C31—C32—C27 119.7 (13)


S44

P5—Pt1—Br2 86.69 (8) C31—C32—H32 120.2

P4—Pt1—Br2 88.80 (8) C27—C32—H32 120.2

Br3—Pt1—Br2 178.06 (5) P4—C34—H34A 109.5

C34—P4—C6 99.0 (6) P4—C34—H34B 109.5

C34—P4—C35 104.8 (6) H34A—C34—H34B 109.5

C6—P4—C35 103.1 (6) P4—C34—H34C 109.5

C34—P4—Pt1 117.4 (4) H34A—C34—H34C 109.5

C6—P4—Pt1 104.0 (4) H34B—C34—H34C 109.5

C35—P4—Pt1 124.4 (4) C36—C35—C37 109.6 (11)

C15—P5—C39 101.3 (6) C36—C35—C38 107.3 (10)

C15—P5—C40 104.2 (6) C37—C35—C38 110.9 (10)

C39—P5—C40 103.5 (5) C36—C35—P4 111.3 (9)

C15—P5—Pt1 106.2 (4) C37—C35—P4 111.8 (8)

C39—P5—Pt1 116.6 (4) C38—C35—P4 105.8 (8)

C40—P5—Pt1 122.4 (4) C35—C36—H36A 109.5

N7—C6—C15 122.7 (11) C35—C36—H36B 109.5

N7—C6—P4 116.4 (10) H36A—C36—H36B 109.5

C15—C6—P4 120.9 (9) C35—C36—H36C 109.5

C6—N7—C8 115.6 (11) H36A—C36—H36C 109.5

N7—C8—C13 121.5 (11) H36B—C36—H36C 109.5

N7—C8—C9 116.8 (13) C35—C37—H37A 109.5

C13—C8—C9 121.7 (12) C35—C37—H37B 109.5

C10—C9—C8 116.5 (14) H37A—C37—H37B 109.5

C10—C9—H9 121.8 C35—C37—H37C 109.5

C8—C9—H9 121.8 H37A—C37—H37C 109.5

C9—C10—C11 124.0 (13) H37B—C37—H37C 109.5

C9—C10—H10 118.0 C35—C38—H38A 109.5

C11—C10—H10 118.0 C35—C38—H38B 109.5


S45

C12—C11—C10 119.5 (13) H38A—C38—H38B 109.5

C12—C11—H11 120.3 C35—C38—H38C 109.5

C10—C11—H11 120.3 H38A—C38—H38C 109.5

C11—C12—C13 119.5 (15) H38B—C38—H38C 109.5

C11—C12—H12 120.2 P5—C39—H39A 109.5

C13—C12—H12 120.2 P5—C39—H39B 109.5

N14—C13—C8 122.8 (10) H39A—C39—H39B 109.5

N14—C13—C12 118.6 (12) P5—C39—H39C 109.5

C8—C13—C12 118.7 (12) H39A—C39—H39C 109.5

C15—N14—C13 117.3 (11) H39B—C39—H39C 109.5

N14—C15—C6 119.8 (11) C41—C40—C42 113.0 (11)

N14—C15—P5 119.1 (9) C41—C40—C43 109.8 (12)

C6—C15—P5 121.1 (9) C42—C40—C43 107.4 (10)

C17—C16—C21 113.8 (10) C41—C40—P5 109.0 (8)

C17—C16—Pt1 124.2 (9) C42—C40—P5 107.7 (9)

C21—C16—Pt1 121.9 (8) C43—C40—P5 109.8 (9)

C18—C17—F22 115.0 (11) C40—C41—H41A 109.5

C18—C17—C16 123.4 (12) C40—C41—H41B 109.5

F22—C17—C16 121.6 (10) H41A—C41—H41B 109.5

C17—C18—C19 121.0 (12) C40—C41—H41C 109.5

C17—C18—F23 120.2 (12) H41A—C41—H41C 109.5

C19—C18—F23 118.7 (11) H41B—C41—H41C 109.5

C20—C19—C18 118.3 (11) C40—C42—H42A 109.5

C20—C19—F24 120.8 (12) C40—C42—H42B 109.5

C18—C19—F24 120.6 (12) H42A—C42—H42B 109.5

C19—C20—F25 121.7 (11) C40—C42—H42C 109.5

C19—C20—C21 120.2 (12) H42A—C42—H42C 109.5

F25—C20—C21 118.0 (11) H42B—C42—H42C 109.5


S46

F26—C21—C16 122.6 (9) C40—C43—H43A 109.5

F26—C21—C20 114.3 (10) C40—C43—H43B 109.5

C16—C21—C20 123.0 (11) H43A—C43—H43B 109.5

C28—C27—C32 117.4 (11) C40—C43—H43C 109.5

C28—C27—Pt1 123.0 (9) H43A—C43—H43C 109.5

C32—C27—Pt1 119.5 (9) H43B—C43—H43C 109.5

C27—C28—C29 121.1 (13) All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Data collection: Collect, Nonius B.V.; cell refinement: DENZO; data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR97; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997)


S47

References (1) Parr, R. G.; Yang, W. Density-functional theory of atoms and molecules; Oxford University

Press: Oxford, 1989.

(2) Perdew, J. P. ; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.

(3) Laikov, D. N. Chem. Phys. Lett. 1997, 281, 151.

(4) Laikov, D. N.; Ustynyuk, Yu. A. Russ. Chem. Bulletin 2005, 54, 820.

(5) Stevens, W. J.; Basch, H.; Krauss, M. J. Chem. Phys. 1984, 81, 6026; Stevens, W. J.; Basch, H.;

Krauss, M.; Jasien, P. Can. J. Chem. 1992, 70, 612; Cundari, T. R.; Stevens, W. J. J. Chem. Phys.

1993, 98, 5555.

(6) Schrodinger Inc. (2009) JAGUAR (Schrodinger Inc., Portland, OR), Version 7.6.

(7) (a) Y. Marcus, Ion Solvation. Wiley, Chichester, 1985; (b) J. Richardi, P.H. Fries, H. Krienke, J.

Chem. Phys. 1998, 108, 4079.

(8). (a) Clark, H. C.; Manzer, L. E. J. Organomet. Chem. 1973, 59, 411. (b) Eaborn, C.; Odell, K. J.;

Pidcock, A. J. Chem. Soc., Dalton Trans. 1978, 357. (c) Johnson D. K.; Rukachaisirikul, T.; Sun, Y.;

Taylor, N.J.; Canty, A.J.; Carty, A.J. Inorg. Chem., 1993, 32, 5544.


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