Structural Variation, Π-Charge Transfer, and Transmission of Electronic Substituent Effects

Structural variation, π-charge transfer, and transmission of electronic substituent effects in (E)-β-substituted styrenes: a quantum chemical studyBy Anna Rita CampanelliSUPPLEMENTARY MATERIAL1 Table S1 Selected internal coordinates of the benzene ring and PhC bond distances in (E)-β-substituted styrenes, from B3LYP/6-311++G** calculationsa,b,cSubstituentd,e     r(PhC)H 117.950 121.073 120.225 119.454 1.4721Li 117.317 121.448 120.334 119.120 1.4821BH2(c) 118.196 120.920 120.097 119.771 1.4635BH2(o) 117.792 121.160 120.268 119.352 1.4726 BH3 116.175 121.950 120.745 118.435 1.4642 CH2 (c) 118.909 120.263 119.629 121.309 1.4033 CH2 (c) 114.209 122.574 121.736 117.170 1.4164 CH2 p) 116.114 121.972 120.757 118.430 1.4635Me 117.688 121.200 120.305 119.301 1.4709CF3 118.297 120.861 120.155 119.673 1.4662Ph(c) 117.673 121.186 120.305 119.347 1.4658Ph(o) 117.866 121.110 120.257 119.402 1.4717CHO(c) 118.270 120.862 120.126 119.754 1.4614COMe(c) 118.119 120.954 120.150 119.675 1.4620COCl(c) 118.379 120.790 120.101 119.840 1.4585 COO (c) 116.978 121.567 120.492 118.904 1.4673 COO (o) 116.642 121.714 120.634 118.664 1.4641COOH(c) 118.236 120.887 120.136 119.719 1.4620COOMe(c) 118.174 120.923 120.151 119.680 1.4628CCH 117.921 121.048 120.250 119.485 1.46372 Table S1, continuedCN 118.258 120.864 120.158 119.700 1.4621 NH (c) 114.450 122.506 121.603 117.333 1.4229NH2(c) 117.104 121.448 120.544 118.914 1.4627NH2(p) 117.778 121.143 120.287 119.362 1.4702NF2(p) 118.428 120.773 120.132 119.762 1.4630 NH3 118.961 120.433 120.015 120.143 1.4567NO2(c) 118.465 120.739 120.105 119.850 1.4593NO2(o) 118.356 120.818 120.186 119.638 1.4672NC 118.124 120.929 120.220 119.579 1.4633 N2 119.119 120.225 119.799 120.836 1.4228 O 114.674 122.456 121.455 117.504 1.4308OH(c) 117.566 121.219 120.426 119.146 1.4673OMe(c) 117.457 121.284 120.432 119.112 1.4689 OH2 (p) 119.157 120.302 119.993 120.255 1.4544F 117.937 121.032 120.320 119.362 1.4685Na 117.306 121.452 120.349 119.093 1.4838MgCl 117.894 121.121 120.206 119.453 1.4778SiH3 118.006 121.043 120.194 119.521 1.4719SiMe3 117.881 121.115 120.224 119.443 1.4734PH2(p) 118.043 121.016 120.201 119.526 1.4712 PH3 118.934 120.430 119.923 120.359 1.4462 S 115.606 122.101 121.064 118.066 1.4454SH(c) 117.723 121.149 120.348 119.283 1.4681Cl 118.038 120.982 120.273 119.452 1.46933 Table S1, continuedClO3 118.761 120.572 120.109 119.877 1.4643Br 118.058 120.974 120.265 119.466 1.4706 range 4.948 2.349 2.107 4.139 0.0805 a The geometry of the benzene ring has been made consistent with C2v symmetry by averaging appropriate geometrical parameters. Bond angles are labeled according to Fig. 1. b Bond angles are in degrees, bond distances in Å. c The small intervals of values spanned by some of the ring angles and the correlation introduced by geometrical constraints make it preferable to present bond angles with three decimal figures. Using only two would artificially lower some of the correlations, without otherwise affecting the results of the present study. d The conformation of non-linear substituents with respect to the symmetry plane is denoted as coplanar (c), orthogonal (o), and pyramidal (p) according to   the definitions given in the text. In the XY3 groups (BH3 , Me, CF3, NH3 , SiH3, SiMe3, PH3 , and ClO3) one of the XY bonds is antiperiplanar to the C=C bond.In the pyramidal groups XY2E (where E is a lone pair of electrons), namely   CH2 (p), NH2(p) , NF2(p), OH2 (p), and PH2(p), the lone pair axis is  synperiplanar to the C=C bond. In the angular XYE2 groups (NH (c), OH(c), OMe(c), and SH(c)) the XY bond is synperiplanar to the C=C bond. In the CHO(c) group the C=O bond is antiperiplanar to the C=C bond. In the COMe(c), COCl(c), COOH(c), and COOMe(c) groups the C=O bond is synperiplanar to the C=C bond. e The non-resonant substituents through which the least-squares line of Fig. 2 has been traced are identified in bold.4 Table S2 π-Charges brought about by the substituent on the vinylene spacer, phenyl probe, and whole styrene frame of (E)-β-substituted styrenesa b STY c STY d STY e Substituent ΔqA ΔqB ΔqABH 0.009 0.011 0.002Li 0.033 0.024 0.009BH2(c) 0.102 0.069 0.171BH2(o) 0.022 0.001 0.023 BH3 0.064 0.123 0.059 CH2 (c) 0.282 0.445 0.727 CH2 (c) 0.265 0.411 0.676 CH2 p) 0.045 0.116 0.071Me 0.008 0.006 0.014CF3 0.007 0.044 0.037Ph(c) 0.004 0.004 0.000Ph(o) 0.005 0.006 0.001CHO(c) 0.056 0.058 0.114COMe(c) 0.049 0.051 0.100COCl(c) 0.053 0.077 0.130COO(c) 0.054 0.057 0.003COO(o) 0.003 0.097 0.094COOH(c) 0.039 0.054 0.093COOMe(c) 0.037 0.047 0.084CCH 0.005 0.020 0.0155 Table S2, continuedCN 0.002 0.049 0.047NH(c) 0.211 0.357 0.568NH2(c) 0.126 0.069 0.195NH2(p) 0.013 0.001 0.012NF2(p) 0.012 0.053 0.065 NH3 0.104 0.118 0.014NO2(c) 0.027 0.071 0.098NO2(o) 0.053 0.030 0.023NC 0.026 0.027 0.001 N2 0.008 0.304 0.312O 0.135 0.303 0.438OH(c) 0.094 0.036 0.130OMe(c) 0.106 0.039 0.145 OH2 (p) 0.118 0.129 0.011F 0.067 0.008 0.075Na 0.036 0.033 0.003MgCl 0.006 0.016 0.010SiH3 0.005 0.024 0.019SiMe3 0.001 0.015 0.016PH2(p) 0.015 0.022 0.007 PH3 (a) 0.091 0.176 0.085S 0.152 0.212 0.364SH(c) 0.110 0.016 0.126Cl 0.081 0.006 0.0756 Table S2, continuedClO3 0.061 0.064 0.003Br 0.076 0.009 0.067 a π-Charges are in electrons; they have been obtained by NAO analysis at the B3LYP/6-311++G** level of theory. b The non-resonant substituents through which the least-squares line of Fig. 2 has been traced are identified in bold. c Substituent-induced π-charge on the vinylene spacer. d Substituent-induced π-charge on the phenyl probe. e STY STY STY ΔqAB = ΔqA  ΔqB is the total π-charge transferred from the substituent into the styrene frame, or vice versa.7 Table S3 Multiple regression statistics for the structural substituent STY parameter SF versus field, resonance, and electronegativity parametersa b 2 c 2 d e f Explanatory variables R Radj F PBCO SF 0.8151 0.8109 194.01 <0.0001BCO SF , SR 0.9429 0.9403 355.08 <0.0001BCO SF , SR, SE 0.9776 0.9760 611.72 <0.0001BCO BCO 2 SF , SR, SE, (SF ) 0.9929 0.9922 1429.81 <0.0001BCO BCO 2 2 SF , SR, SE, (SF ) , SR 0.9963 0.9959 2163.79 <0.0001 a STY The SF values have been calculated at the B3LYP/6-311++G** level of theory and refer to 46 (E)--substituted styrenes. b The sources of the values used for the explanatory variables are specified in the text. c Multiple correlation coefficient, squared. d Adjusted multiple correlation coefficient, squared. e Fisher test of variance for overall correlation. f STY Probability of being wrong in concluding that there is an association between SF and the explanatory variables.8 Table S4 Substituent-induced π-charges on the spacer (ring A) and probe (ring B) of two coplanar 4- substituted biphenylsBIPH(c) BIPH(c) BIPH(c) Substituent ΔqA ΔqB ΔqABNH(c) 0.309 0.233 0.542Br 0.051 0.004 0.055π-Charges are in electrons; they have been obtained by NAO BIPH(c) analysis at the B3LYP/6-311++G** level of theory. ΔqA and BIPH(c) ΔqB are the substituent-induced π-charges on ring A and ring B, BIPH(c) BIPH(c) BIPH(c) respectively. ΔqAB = ΔqA + ΔqB is the total -charge transferred from the substituent into the biphenyl frame.9

Structural Variation, Π-Charge Transfer, and Transmission of Electronic Substituent Effects

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