SUPPORTING INFORMATION FOR: Trialkylstibine complexes of boron, aluminium, gallium and indium trihalides: synthesis, properties and bonding Victoria K. Greenacre, William Levason and Gillian Reid Chemistry, University of Southampton, Southampton SO17 1BJ. U.K. Supporting Information Table S1: X-ray crystallographic data S2 Computational details S6 Table S2 Bond lengths and angles for optimised free ligands: S7 Table S3 NBO data for free ligands: Sb-C bonds S7 Table S4 Bond lengths and angles of optimised structures: S8 Table S5 NBO data for optimised coordination complexes: Sb-C bonds S11 Table S6 NBO data for optimised coordination complexes: Sb-M bonds S12 Table S7 NBO natural charges of the complexes compared to the individual components MX 3 or the SbR 3 S13 Table S8 Frontier Molecular Orbitals for [MX 3 (SbR 3 )] complexes Figure S1 [BCl 3 (Sb i Pr 3 )] Figure S2 [BBr 3 (SbEt 3 )] Figure S3 [BBr 3 (Sb i Pr 3 )] Figure S4 [BI 3 (SbEt 3 )] Figure S5 [BI 3 (Sb i Pr 3 )] Figure S6 [AlCl 3 (SbEt 3 )] Figure S7 [AlCl 3 (Sb i Pr 3 )] Figure S8 [AlBr 3 (SbEt 3 )] Figure S9 [AlBr 3 (Sb i Pr 3 )] Figure S10 [All 3 (SbEt 3 )] Figure S11 [AlI 3 (SbiPr 3 )] Figure S12 [GaCl 3 (SbEt 3 )] Figure S13 [GaCl 3 (Sb i Pr 3 )] Figure S14 [GaBr 3 (SbEt 3 )] Figure S15 [GaBr 3 (Sb i Pr 3 )] Figure S16 [GaI 3 (SbEt 3 )] Figure S17 [GaI 3 (Sb i Pr 3 )] Figure S18 [InCl 3 (SbEt 3 )] Figure S19 [InCl 3 (Sb i Pr 3 )] Figure S20 [InBr 3 (SbEt 3 )] Figure S21 [InBr 3 (Sb i Pr 3 )] Figure S22 [InI 3 (SbEt 3 )] Figure S23 [InI 3 (Sb i Pr 3 )] S14 S16 S17 S19 S20 S22 S23 S24 S26 S27 S29 S31 S33 S35 S37 S39 S41 S42 S44 S46 S47 S48 S51 S53 S1
Table S1 X-ray crystallographic data a Compound [BBr 3 (SbEt 3 )] [BBr 3 (Sb i Pr 3 )] [BCl 3 (Sb i Pr 3 )] Formula C 6 H 15 BBr 3 Sb C 9 H 21 BBr 3 Sb C 9 H 21 BCl 3 Sb M 459.47 501.55 368.15 Crystal system orthorhombic monoclinic monoclinic Space group (no.) Pna2 1 (33) P2 1 /c(14) P2 1 /c(14) a /Å 25.8381(3) 15.2669(5) 14.9862(9) b /Å 13.2288(1) 15.5639(4) 15.2594(5) c /Å 7.4987(1) 14.3106(5) 14.1726(8) α / 90 90 90 β / 90 113.927(4) 115.667(7) γ / 90 90 90 U /Å 3 2563.11(5) 3108.16(19) 2921.2(3) Z 8 8 8 µ(mo-k α )/mm 1 11.456 9.457 2.404 F(000) 1696 1888 1456 Total number reflns 42972 66360 18502 R int 0.037 0.081 0.076 Unique reflns 5043 6100 5743 No. of params, restraints 206, 7 265, 0 265, 0 GOF 1.088 1.171 1.057 R 1, wr 2 [I > 2σ(I)] b 0.024, 0.049 0.064,0.133 0.050, 0.126 R 1, wr 2 (all data) 0.027, 0.050 0.088,0.151 0.068, 0.140 a Common items: T = 293 K; wavelength (Mo-K α ) = 0.71073 Å; θ(max) = 27.5 ; b R 1 = Σ F o - F c /Σ F o ; wr 2 =[Σw(F o 2 -F c 2 ) 2 /ΣwF o 4 ] 1/2 S2
Compound [BI 3 (SbEt 3 )] [BI 3 (Sb i Pr 3 )] [AlI 3 (Sb i Pr 3 )] Formula C 6 H 15 BI 3 Sb C 9 H 21 BI 3 Sb C 9 H 21 AlI 3 Sb M 600.48 642.5 658.69 Crystal system monoclinic orthorhombic monoclinic Space group (no.) P2 1 /c(14) P2 1 2 1 2 1 (19) Cc(9) a /Å 8.1078(2) 13.5920(2) 11.6976(7) b /Å 13.0295(2) 16.0773(2) 10.6980(5) c /Å 13.5565(3) 23.2796(3) 14.5177(7) α / 90 90 90 β / 102.601(2) 90 98.526(5) γ / 90 90 90 U /Å 3 1397.62(5) 5087.12(12) 1796.68(16) Z 4 4 4 µ(mo-k α )/mm 1 8.555 7.061 6.714 F(000) 1057 3480 1192 Total number reflns 44009 87200 10734 R int 0.030 0.029 0.079 Unique reflns 2738 9990 3265 No. of params, restraints 103, 0 398, 0 133, 2 GOF 1.000 1.017 1.079 R 1, wr 2 [I > 2σ(I)] b 0.018, 0.046 0.014, 0.033 0.052, 0.133 R 1, wr 2 (all data) 0.019, 0.046 0.014, 0.034 0.056, 0.138 S3
Compound [GaCl 3 (Sb i Pr 3 )] [GaBr 3 (SbEt 3 )] [GaI 3 (Sb i Pr 3 )] Formula C 9 H 21 Cl 3 GaSb C 6 H 15 Br 3 GaSb C 9 H 21 GaI 3 Sb M 427.08 518.38 701.43 Crystal system monoclinic monoclinic monoclinic Space group (no.) P2 1 /n(14) P2 1 /n(14) Cc (9) a /Å 8.3258(1) 8.2065(5) 11.6649(6) b /Å 14.3517(4) 11.8947(5) 10.7276(6) c /Å 13.3957(2) 14.0799(10) 14.4102(7) α / 90 90 90 β / 96.550(1) 102.434(7) 98.536(6) γ / 90 90 90 U /Å 3 1590.20(5) 1342.16(14) 1783.27(16) Z 4 4 4 µ(mo-k α )/mm 1 3.866 12.904 8.193 F(000) 832 952 1264 Total number reflns 10533 38882 5335 R int 0.040 0.143 0.041 Unique reflns 3128 2631 3219 No. of params, restraints 133, 0 103, 0 121, 104 GOF 0.817 1.132 0.922 R 1, wr 2 [I > 2σ(I)] b 0.032, 0.103 0.055, 0.138 0.028, 0.048 R 1, wr 2 (all data) 0.036, 0.109 0.066, 0.147 0.032, 0.050 S4
Compound [InCl 3 (Sb i Pr 3 )] [InCl 3 (SbEt 3 )] [InI 3 (Sb i Pr 3 )] Formula C 9 H 21 Cl 3 InSb C 6 H 15 Cl 3 InSb C 9 H 21 I 3 InSb M 472.18 430.10 746.56 Crystal system monoclinic triclinic monoclinic Space group (no.) P2 1 /n(14) P-1 (1) Cc (9) a /Å 8.6108(4) 8.4984(7) 11.7126(1) b /Å 21.7651(7) 8.8133(7) 10.8918(1) c /Å 9.3198(3) 8.8597(8) 14.6010(2) α / 90 88.135(7) 90 β / 116.041(5) 86.072(7) 99.608(1) γ / 90 84.455(6) 90 U /Å 3 1569.35(12) 658.70(10) 1836.54(4) Z 4 2 4 µ(mo-k α )/mm 1 3.670 4.361 7.744 F(000) 904 404 1326 Total number reflns 20018 8442 7833 R int 0.032 0.095 0.019 Unique reflns 3092 2588 3137 No. of params, restraints 152, 0 103, 0 133, 2 GOF 1.110 1.227 1.032 R 1, wr 2 [I > 2σ(I)] b 0.018, 0.036 0.090, 0.145, 0.018, 0.039 R 1, wr 2 (all data) 0.021, 0.036 0.114, 0.156 0.019, 0.039 S5
Compound [InI 3 (SbEt 3 )] Formula C 6 H 15 I 3 InSb M 704.48 Crystal system monoclinic Space group (no.) P2 1 /n(14) a /Å 8.5207(1) b /Å 12.5754(2) c /Å 14.7187(2) α / 90 β / 102.914(1) γ / 90 U /Å 3 1537.24(4) Z 4 µ(mo-k α )/mm 1 9.242 F(000) 1230 Total number reflns 13653 R int 0.023 Unique reflns 3018 No. of params, restraints 103, 0 GOF 1.030 R 1, wr 2 [I > 2σ(I)] b 0.017, 0.041 R 1, wr 2 (all data) 0.018, 0.041 Computational details Calculations were performed using Gaussian 09W, Revision C.01,39 running on an Intel Core i5-2500 (quad, 3.3 GHz), equipped with 4 GB RAM; results were visualized using GaussView 5.0. Geometry optimisation and frequency calculations were performed on the isolated molecules, and using the B3LYP hybrid density functional, using a basis set with a Stuttgart-Dresden effective core potential on Ga, In, Sb, B and I atoms, with double zeta basis set on H, C, Al and Cl atoms. Minima were characterized by frequency calculations at the same level of theory. NBO calculations were performed at the same level of theory. For the frequency calculation of [InI 3 (SbEt 3 )], there is a small imaginary frequency at 1.56i cm -1 which we conclude is an artefact of the code as a result of the ease of rotation of the InI 3 fragment. S6
The supplemental file [MX3(SbR3)].xyz contains the computed Cartesian coordinates of all complexes and free stibine ligands and metal halides. The file may be opened as a text file to read the coordinates, or opened directly by a molecular modelling program such as Mercury (version 3.3 or later, http://www.ccdc.cam.ac.uk/pages/home.aspx) for visualization and analysis. Table S2 Bond lengths/angles for optimised free ligands: Me 3 Sb Sb-C 2.1848 2.1843 2.1846 C-Sb-C 94.773 94.773 94.753 Et 3 Sb 2.2014 2.1972 2.1972 96.712 96.712 94.578 i Pr 3 Sb 2.2282 2.2133 2.2206 100.234 97.211 96.831 t Bu 3 Sb 2.2621 2.2617 2.2609 103.395 103.355 103.346 Table S3 NBO data for free ligands: Sb-C bonds Contribution (%) Breakdown of Sb contributions (%) Breakdown of C contributions (%) Sb C s p s p Et 3 Sb 31.18 31.17 31.18 68.82 68.83 68.82 10.66 10.77 10.66 89.34 89.23 89.34 20.42 20.57 20.42 79.58 79.43 79.58 i Pr 3 Sb 31.12 31.23 30.99 68.88 68.77 69.01 11.02 10.86 10.79 88.98 89.14 89.21 18.85 18.97 19.20 81.15 81.03 80.80 Me 3 Sb 30.71 30.71 30.70 69.29 69.29 69.30 10.35 10.35 10.36 89.65 89.65 89.64 22.09 22.08 22.09 77.91 77.92 77.91 t Bu 3 Sb 30.48 30.49 30.50 69.52 69.51 69.50 11.26 11.24 11.24 88.74 88.76 88.76 17.78 17.77 17.76 82.22 82.23 82.24 S7
Table S4 Bond lengths and angles of optimised structures [BCl 3 (Sb i Pr 3 )] DFT X-ray 1 X-ray 2 Sb-B 2.3019 2.272(7) 2.282(7) B-Cl 1.9146 1.9137 1.9149 1.839(7) 1.834(7) 1.843(7) 1.834(7) 1.832(7) 1.838(7) Sb-C 2.186(av) 2.146(av) 2.142(av) Cl-B-Cl 112.016 111.030 11.523 111.1(4) 111.0(4) 110.9(4) 110.4(4) 111.7(4) 111.5(4) Cl-B-Sb 106.980 107.137 107.883 106.5(3) 107.2(3) 110.0(3) 109.6(3) 104.0(3) 109.4(3) C-Sb-C 105.919(av) 106.5(av) 104.6(av) [BBr 3 (Sb i Pr 3 )] BBr 3 (SbEt 3 )] X-ray X-ray DFT Molecule 1 Molecule 2 Molecule 1 Molecule 2 DFT Sb-B 2.264(14) 2.250(13) 2.3171 2.266(9) 2.241(9) 2.3018 B-Br 2.003(14) 1.995(15) 2.026(15) 2.001(15) 2.012(15) 2.020(14) 2.0697 2.0809 2.0676 1.999(8) 2.013(8) 2.012(9) 2.003(8) 2.009(8) 2.020(8) 2.0686 2.0720 2.0699 Sb-C 2.157 (av) 2.147(av) 2.192(av) 2.132(av) 2.134(av) 2.159(av) 110.3(7) 111.1(6) 111.643 111.5(4) 111.3(4) 112.084 Br-B- 110.2(7) 110.2(7) 111.373 110.8(4) 110.4(4) 111.818 Br 111.3(6) 110.1(6) 110.596 111.1(4) 111.7(4) 111.833 109.8(6) 110.5(6) 108.585 107.3(4) 109.1(4) 107.451 Br-B- 110.8(6) 107.5(7) 105.233 107.1(4) 108.4(4) 106.042 Sb 104.3(6) 107.4(6) 109.214 108.9(4) 105.7(4) 107.218 C-Sb-C 104.5 (av) 106.6 (av) 103.878(av) 106.2 (av) 108.0 (av) 104.785(av) [BI 3 (Sb i Pr 3 )] BI 3 (SbEt 3 )] X-ray Molecule 1 Molecule 2 Molecule 3 DFT X-ray DFT Sb-B 2.256(5) 2.255(5) 2.255(5) 2.3061 2.230(4) 2.2874 B-I 2.227(5) 2.244(5) 2.230(5) 2.222(5) 2.241(5) 2.232(5) 2.234(5) 2.239(5) 2.230(5) 2.2948 2.2954 2.2957 2.234(4) 2.227(4) 2.226(4) 2.2965 2.2858 2.2930 Sb-C 2.159(av) 2.159(av) 2.161(av) 2.196(av) 2.126(av) 2.163(av) I-B-I 110.6(2) 111.0(2) 110.1(2) 111.0(2) 110.5(2) 110.0(2) 109.9(2) 110.7(2) 110.7(2) 2.295 2.296 2.295 111.59(17) 110.61(17) 112.27(17) 111.388 112.142 111.944 I-B-Sb 106.9(2) 108.7(2) 109.6(2) 109.5(2) 108.1(2) 107.6(2) 108.7(2) 108.2(2) 108.7(2) 107.991 107.932 107.858 106.29(16) 105.89(17) 109.91(17) 105.648 109.160 106.177 C-Sb-C 105.233(av) 105.37(av) 105.38(av) 103.062(av) 105.88(av) 104.725(av) S8
[AlI 3 (Sb i Pr 3 )] DFT X-ray Sb-Al 2.7676 2.680(9) Al-I 2.6207 2.6190 2.6112 2.525(9) 2.507(10) 2.509(9) Sb-C 2.193(av) 2.173(av) 114.271 111.4(4) I-Al-I 113.993 112.0(4) 113.662 I-Al-Sb 102.959 107.115 103.300 104.8(3) 109.4(3) 104.8(3) C-Sb-C 105.042(av) 104.13(av) [GaCl 3 (Sb i Pr 3 )] DFT X-ray Sb-Ga 2.7204 2.6297(5) Ga-Cl 2.2686 2.2731 2.2746 2.1738(12) 2.1730(12) 2.1811(12) Sb-C 2.188(av) 2.158(av) Cl-Ga-Cl 114.078 114.398 114.227 110.12(5) 109.87(5) 109.53(5) Cl-Ga-Sb 106.595 101.906 103.903 106.29(4) 112.63(4) 108.33(3) C-Sb-C 105.732 106.137(av) [GaBr 3 (SbEt 3 )] DFT X-ray Sb-Ga 2.7621 2.6166(10) Ga-Br 2.4061 2.4077 2.4064 2.3181(12) 2.3105(13) 2.3117(12) Sb-C 2.167(av) 2.11(av) 114.618 109.97(5) 114.718 111.84(5) 114.510 109.54(5) Br-Ga-Br Br-Ga-Sb 104.390 102.580 103.962 108.16(4) 106.89(4) 110.35(4) C-Sb-C 103.487(av) 104.5(av) S9
[GaI 3 (Sb i Pr 3 )] DFT Data DFT X-ray Sb-Ga 2.7822 2.6396(14) Ga-I 2.6313 2.6315 2.6223 2.5379(14) 2.5482(14) 2.5375(15) Sb-C 2.195(av) 2.147(av) I-Ga-I 113.644 114.081 113.501 110.02(5) 113.08(5) 110.24(5) I-Ga-Sb 104.163 102.640 107.454 106.10(5) 111.20(5) 106.09(5) C-Sb-C 104.35(av) 105.3(av) [InCl 3 (Sb i Pr 3 )] [InCl 3 (SbEt 3 )] DFT X-ray DFT X-ray Sb-In 2.8708 2.7772(3) 2.8917 2.7713(13) In-Cl 2.2373 2.3946 2.3987 2.3659(6) 2.3739(6) 2.3523(6) 2.3932 2.3925 2.3941 2.376(4) 2.394(4) 2.379(3) Sb-C 2.189(av) 2.165(av) 2.166(av) 2.126(av) Cl-In-Cl 115.386 114.896 115.506 104.26(2) 111.92(2) 105.55(2) 115.649 115.551 115.518 103.04(13) 105.63(13) 112.30(13) Cl-In-Sb 104.812 102.412 101.062 115.507(17) 106.531(17) 112.091(17) 102.686 101.423 102.865 111.01(10) 109.66(9) 114.53(10) C-Sb-C 105.478(av) 107.02(av) 103.85(av) 104.1 (av) [InI 3 (Sb i Pr 3 )] [InI 3 (SbEt 3 )] DFT X-ray DFT X-ray Sb-In 2.9248 2.8049(3) 2.9278 2.8121(3) In-I 2.7463 2.7449 2.7390 2.71224(17) 2.7051(4) 2.7000(3) 2.7387 2.7389 2.7408 2.6961(3) 2.7207(3) 2.7073(3) Sb-C 2.196(av) 2.168(av) 2.169(av) 2.137(av) I-In-I 114.518 114.330 114.809 112.552(14) 109.917(7) 109.569(10) 115.486 115.694 115.565 110.380(9) 110.996(9) 106.843(9) I-In-Sb 101.377 103.365 106.419 106.045(9) 106.662(8) 112.051(14) 102.755 103.034 101.144 110.985(9) 105.627(9) 111.793(9) C-Sb-C 104.220(av) 106.2 (av). 102.867(av) 103.7(av) S10
Table S5 NBO data for optimised coordination complexes: Sb-C bonds Contribution (%) Breakdown of Sb contributions (%) Breakdown of C contributions (%) Sb C s p s p [BCl 3 (Sb i Pr 3 )] 34.84 34.68 34.57 65.16 65.32 65.43 23.41 23.44 22.92 76.59 76.56 77.08 17.76 17.90 17.92 82.24 82.10 82.08 [BBr 3 (Sb i Pr 3 )] 34.77 34.77 34.84 65.23 65.23 65.16 23.43 23.03 22.75 76.57 76.97 77.25 17.86 17.85 17.87 82.14 82.15 82.13 [BBr 3 (SbEt 3 )] 34.72 34.80 34.75 65.28 65.20 65.25 22.92 22.73 22.77 77.08 77.27 77.23 19.62 19.65 19.65 80.38 80.35 80.35 [BI 3 (Sb i Pr 3 )] 34.85 34.84 34.87 65.15 65.16 65.13 22.91 22.89 22.88 77.09 77.11 77.12 17.93 17.92 17.90 82.07 82.08 82.10 [BI 3 (SbEt 3 )] 34.74 34.92 34.89 65.26 65.08 65.11 22.06 22.92 23.02 77.94 77.08 76.98 19.85 19.65 19.69 80.15 80.35 80.31 [AlI 3 (Sb i Pr 3 )] 35.83 35.90 35.89 64.17 64.10 64.11 23.27 24.50 24.44 76.73 75.50 75.56 17.61 17.41 17.47 82.39 82.59 82.53 [GaCl 3 (Sb i Pr 3 )] 36.00 35.75 35.89 64.00 64.25 64.11 24.94 24.10 24.60 75.06 75.90 75.40 17.29 17.51 17.29 82.71 82.49 82.71 [GaBr 3 (SbEt 3 )] 35.55 35.62 35.62 64.45 64.38 64.38 23.82 23.93 23.69 76.15 76.07 76.31 19.16 19.23 19.16 80.84 80.77 80.82 [GaI 3 (Sb i Pr 3 )] 35.81 35.67 35.48 64.19 64.33 64.52 24.42 24.21 23.37 75.58 75.79 76.63 17.39 17.35 17.63 82.61 82.65 82.37 [InCl 3 (Sb i Pr 3 )] 36.01 36.13 36.25 63.99 63.87 63.75 24.84 25.08 25.41 75.16 74.92 74.59 17.40 17.18 17.19 82.60 82.82 82.81 [InCl 3 (SbEt 3 )] 36.06 36.05 36.08 63.94 63.95 63.92 24.72 24.63 24.69 75.28 75.37 75.31 19.08 18.92 18.98 80.92 81.08 81.02 [InI 3 (Sb i Pr 3 )] 35.72 36.00 35.84 64.28 64.00 64.16 23.92 24.73 24.46 76.08 75.27 75.54 17.50 17.26 17.26 82.50 82.74 82.74 [InI 3 (SbEt 3 )] 35.63 35.56 35.64 64.37 64.44 64.36 23.72 23.86 23.97 76.28 76.14 76.03 19.17 19.15 19.22 80.83 80.85 80.78 S11
Table S6 NBO data for optimised coordination complexes: Sb-M bonds Contribution (%) Breakdown of Sb contributions (%) Breakdown of M contributions (%) Sb M s p s p [BCl 3 (Sb i Pr 3 )] [BBr 3 (Sb i Pr 3 )] [BBr 3 (SbEt 3 )] 52.02 47.98 30.26 69.74 25.59 74.41 51.00 49.00 30.80 69.20 24.89 75.11 51.48 48.52 31.59 68.41 24.15 75.85 [BI 3 (Sb i Pr 3 )] 48.88 51.12 31.32 68.68 25.68 74.32 [BI 3 (SbEt 3 )] 49.46 50.54 32.00 68.00 25.09 74.91 [AlI 3 (Sb i Pr 3 )] 67.87 32.13 27.82 72.18 19.94 80.06 [GaCl 3 (Sb i Pr 3 )] 71.67 28.33 26.43 73.57 21.13 78.87 [GaBr 3 (SbEt 3 )] 72.17 27.83 28.61 71.39 18.97 81.03 [GaI 3 (Sb i Pr 3 )] 70.31 29.69 28.05 71.95 19.69 80.31 [InCl 3 (Sb i Pr 3 )] 75.57 24.43 24.75 75.25 20.87 79.13 [InCl 3 (SbEt 3 )] 76.28 23.72 26.06 73.96 19.83 80.17 [InI 3 (Sb i Pr 3 )] 74.93 25.07 26.96 73.04 19.27 80.73 [InI 3 (SbEt 3 )] 75.48 24.52 28.53 71.47 18.18 81.82 S12
Table S7 NBO natural charges of the complexes compared to the individual components MX 3 or the SbR 3 [MX 3 (SbR 3 )] MX 3 SbR 3 Bond order Sb M Sb M [BCl 3 (Sb i Pr 3 )] 1.74641 0.04914 1.14065 0.56475 0.8814 [BBr 3 (Sb i Pr 3 )] 1.75597-0.29068 1.14065 0.8762 0.23298 [BBr 3 (SbEt 3 )] 1.75731-0.29054 1.13327 0.8763 [BI 3 (Sb i Pr 3 )] 1.78463-0.74802 1.14065 0.8980-0.21496 [BI 3 (SbEt 3 )] 1.77747-0.74224 1.13327 0.9020 [AlI 3 (Sb i Pr 3 )] 1.40875 0.30973 1.14065 0.66341 0.6977 [GaCl 3 (Sb i Pr 3 )] 1.36333 0.98930 1.14065 1.28586 0.6705 [GaBr 3 (SbEt 3 )] 1.37491 0.78419 1.13327 1.08464 0.6459 [GaI 3 (Sb i Pr 3 )] 1.38449 0.39923 1.14065 0.68600 0.6571 [InCl 3 (Sb i Pr 3 )] 1.28396 1.17952 1.14065 0.6111 1.40392 [InCl 3 (SbEt 3 )] 1.28489 1.17101 1.13327 0.5923 [InI 3 (Sb i Pr 3 )] 1.30023 0.71943 1.14065 0.5961 0.95100 [InI 3 (SbEt 3 )] 1.30913 0.70761 1.13327 0.5842 S13
Table S8 Frontier Molecular Orbitals for [MX 3 (SbR 3 )] complexes HOMO-1 HOMO LUMO [BCl 3 (Sb i Pr 3 )] [BBr 3 (Sb i Pr 3 )] [BBr 3 (SbEt 3 )] [BI 3 (Sb i Pr 3 )] [BI 3 (SbEt 3 )] [AlI 3 (Sb i Pr 3 )] [GaCl 3 (Sb i Pr 3 )] S14
[GaBr 3 (SbEt 3 )] [GaI 3 (Sb i Pr 3 )] [InCl 3 (Sb i Pr 3 )] [InCl 3 (SbEt 3 )] [InI 3 (Sb i Pr 3 )] [InI 3 (SbEt 3 )] S15
Figure S1 [BCl 3 (Sb i Pr 3 )] Figure S1.1 [BCl 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): L = free ligand L Figure S1.2 [BCl 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S1.3 [BCl 3 (Sb i Pr 3 )] 11 B NMR spectrum (CD 2 Cl 2, 298 K): S16
Figure S1.4 [BCl 3 (Sb i Pr 3 )] IR spectrum (Nujol): Figure S2 [BBr 3 (SbEt 3 )] Figure S2.1 [BBr 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 293 K) (* solvent): * S17
Figure S2.2 [BBr 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S2.3 [BBr 3 (SbEt 3 )] 11 B NMR spectrum (CD 2 Cl 2 /CH 2 Cl 2, 293 K): Figure S2.4 [BBr 3 (SbEt 3 )] IR spectrum (Nujol): S18
Figure S3 [BBr 3 (Sb i Pr 3 )] Figure S3.1 [BBr 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S3.2 [BBr 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S19
Figure S3.3 [BBr 3 (Sb i Pr 3 )] 11 B NMR spectrum (CD 2 Cl 2, 298 K): Figure S3.4 [BBr 3 (Sb i Pr 3 )] IR spectrum (Nujol): Figure S4 [BI 3 (SbEt 3 )] Figure S4.1 [BI 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S20
Figure S4.2 [BI 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S4.3 [BI 3 (SbEt 3 )] 11 B NMR spectrum (CD 2 Cl 2, 298 K): S21
Figure S4.4 [BI 3 (SbEt 3 )] IR spectrum (Nujol): Figure S5 [BI 3 (Sb i Pr 3 )] Figure S5.1 [BI 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K) (* = solvent): S22
* Figure S5.2 [BI 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S5.3 [BI 3 (Sb i Pr 3 )] 11 B NMR spectrum (CD 2 Cl 2, 298 K): Figure S5.4 [BI 3 (Sb i Pr 3 )] IR spectrum (Nujol): S23
Figure S6 [AlCl 3 (SbEt 3 )] Figure S6.1 [AlCl 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S6.2 [AlCl 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S24
Figure S6.3 [AlCl 3 (SbEt 3 )] 27 Al NMR spectrum (CD 2 Cl 2, 298 K): = Al in probe Figure S7 [AlCl 3 (Sb i Pr 3 )] Figure S7.1 [AlCl 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S25
Figure S7.2 [AlCl 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S7.3 [AlCl 3 (Sb i Pr 3 )] 27 Al NMR spectrum (CD 2 Cl 2, 298 K): = Al in probe S26
Figure S7.4 [AlCl 3 (Sb i Pr 3 )] IR spectrum (Nujol): Figure S8 [AlBr 3 (SbEt 3 )] Figure S8.1 [AlBr 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): = impurities Figure S8.2 [AlBr 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S27
Figure S8.3 [AlBr 3 (SbEt 3 )] 27 Al NMR spectrum (CD 2 Cl 2, 298 K): = Al in probe, = impurity [AlBr - 4 ] Figure S9 [AlBr 3 (Sb i Pr 3 )] Figure S9.1 [AlBr 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S28
Figure S9.2 [AlBr 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): = impurities Figure S9.3 [AlBr 3 (Sb i Pr 3 )] 27 Al NMR spectrum (CD 2 Cl 2, 298 K): = Al in probe, = impurity [AlBr 4 ] - S29
Figure S9.4 [AlBr 3 (Sb i Pr 3 )] IR spectrum (Nujol): Figure S10 [All 3 (SbEt 3 )] Figure S10.1 [AlI 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S30
Figure S10.2 [AlI 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S10.3 [AlI 3 (SbEt 3 )] 27 Al NMR spectrum (CD 2 Cl 2, 298 K): = Al in probe S31
Figure S11 [AlI 3 (Sb i Pr 3 )] Figure S11.1 [AlI 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S11.2 [AlI 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S32
Figure S11.3 [AlI 3 (Sb i Pr 3 )] 27 Al NMR spectrum (CD 2 Cl 2, 298 K): = Al in probe Figure S11.4 [AlI 3 (Sb i Pr 3 )] IR spectrum (Nujol): S33
Figure S12 [GaCl 3 (SbEt 3 )] Figure S12.1 [GaCl 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S12.2 [GaCl 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S34
Figure S12.3 [GaCl 3 (SbEt 3 )] 171 Ga NMR spectrum (CD 2 Cl 2, 298 K): Figure S12.4 [GaCl 3 (SbEt 3 )] IR spectrum (Nujol): S35
Figure S13 [GaCl 3 (Sb i Pr 3 )] Figure S13.1 [GaCl 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S13.2 [GaCl 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S36
Figure S13.3 [GaCl 3 (Sb i Pr 3 )] 71 Ga NMR spectrum (CD 2 Cl 2, 298 K): Figure S13.4 [GaCl 3 (Sb i Pr 3 )] IR spectrum (Nujol): S37
Figure S14 [GaBr 3 (SbEt 3 )] Figure S14.1 [GaBr 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S14.2 [GaBr 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S38
Figure S14.3 [GaBr 3 (SbEt 3 )] 71 Ga NMR spectrum (CD 2 Cl 2, 298 K): Figure S14.4 [GaBr 3 (SbEt 3 )] IR spectrum (Nujol): S39
Figure S15 [GaBr 3 (Sb i Pr 3 )] Figure S15.1 [GaBr 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S15.2 [GaBr 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S40
Figure S15.3 [GaBr 3 (Sb i Pr 3 )] 71 Ga NMR spectrum (CD 2 Cl 2, 298 K): Figure S15.4 [GaBr 3 (Sb i Pr 3 )] IR spectrum (Nujol): S41
Figure S16 [GaI 3 (SbEt 3 )] Figure S16.1 [GaI 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S16.2 [GaI 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S16.3 [GaI 3 (SbEt 3 )] 71 Ga NMR spectrum (CD 2 Cl 2, 298 K): S42
Figure S16.4 [GaI 3 (SbEt 3 )] IR spectrum (Nujol): Figure S17 [GaI 3 (Sb i Pr 3 )] Figure S17.1 [GaI 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S43
Figure S17.2 [GaI 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S17.3 [GaI 3 (Sb i Pr 3 )] 71 Ga NMR spectrum (CD 2 Cl 2, 298 K): S44
Figure S17.4 [GaI 3 (Sb i Pr 3 )] IR spectrum (Nujol): Figure S18 [InCl 3 (SbEt 3 )] Figure S18.1 [InCl 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S45
Figure S18.2 [InCl 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S18.3 [InCl 3 (SbEt 3 )] IR spectrum (Nujol): S46
Figure S19 [InCl 3 (Sb i Pr 3 )] Figure S19.1 [InCl 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S19.2 [InCl 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S47
Figure S19.3 [InCl 3 (Sb i Pr 3 )] IR spectrum (Nujol): Figure S20 [InBr 3 (SbEt 3 )] Figure S20.1 [InBr 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): S48
Figure S20.2 [InBr 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): Figure S20.3 [InBr 3 (SbEt 3 )] 115 In NMR spectrum (CD 2 Cl 2, 298 K): Figure S20.4 [InBr 3 (SbEt 3 )] IR spectrum (Nujol): S49
Figure S21 [InBr 3 (Sb i Pr 3 )] Figure S21.1 [InBr 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S21.2 [InBr 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): = impurity S50
Figure S21.3 [InBr 3 (Sb i Pr 3 )] 115 In NMR spectrum (CD 2 Cl 2, 298 K): Figure S21.4 [InBr 3 (Sb i Pr 3 )] IR spectrum (Nujol): S51
Figure S22 [InI 3 (SbEt 3 )] Figure S22.1 [InI 3 (SbEt 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S22.2 [InI 3 (SbEt 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S52
Figure S22.3 [InI 3 (SbEt 3 )] 115 In NMR spectrum (CD 2 Cl 2, 298 K): Figure S22.4 [InI 3 (SbEt 3 )] IR spectrum (Nujol): S53
Figure S23 [InI 3 (Sb i Pr 3 )] Figure S23.1 [InI 3 (Sb i Pr 3 )] 1 H NMR spectrum (CD 2 Cl 2, 298 K): Figure S23.2 [InI 3 (Sb i Pr 3 )] 13 C{ 1 H} NMR spectrum (CD 2 Cl 2, 298 K): S54
Figure S23.3 [InI 3 (Sb i Pr 3 )] 115 In NMR spectrum (CD 2 Cl 2, 298 K): Figure S23.4 [InI 3 (Sb i Pr 3 )] IR spectrum (Nujol): S55