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 study

By Anna Rita Campanelli

SUPPLEMENTARY MATERIAL

1 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,c

Substituentd,e     r(PhC)

H 117.950 121.073 120.225 119.454 1.4721

Li 117.317 121.448 120.334 119.120 1.4821

BH2(c) 118.196 120.920 120.097 119.771 1.4635

BH2(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 1.4635

Me 117.688 121.200 120.305 119.301 1.4709

CF3 118.297 120.861 120.155 119.673 1.4662

Ph(c) 117.673 121.186 120.305 119.347 1.4658

Ph(o) 117.866 121.110 120.257 119.402 1.4717

CHO(c) 118.270 120.862 120.126 119.754 1.4614

COMe(c) 118.119 120.954 120.150 119.675 1.4620

COCl(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 1.4641

COOH(c) 118.236 120.887 120.136 119.719 1.4620

COOMe(c) 118.174 120.923 120.151 119.680 1.4628

CCH 117.921 121.048 120.250 119.485 1.4637

2 Table S1, continued

CN 118.258 120.864 120.158 119.700 1.4621

 NH (c) 114.450 122.506 121.603 117.333 1.4229

NH2(c) 117.104 121.448 120.544 118.914 1.4627

NH2(p) 117.778 121.143 120.287 119.362 1.4702

NF2(p) 118.428 120.773 120.132 119.762 1.4630

 NH3 118.961 120.433 120.015 120.143 1.4567

NO2(c) 118.465 120.739 120.105 119.850 1.4593

NO2(o) 118.356 120.818 120.186 119.638 1.4672

NC 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 1.4308

OH(c) 117.566 121.219 120.426 119.146 1.4673

OMe(c) 117.457 121.284 120.432 119.112 1.4689

 OH2 (p) 119.157 120.302 119.993 120.255 1.4544

F 117.937 121.032 120.320 119.362 1.4685

Na 117.306 121.452 120.349 119.093 1.4838

MgCl 117.894 121.121 120.206 119.453 1.4778

SiH3 118.006 121.043 120.194 119.521 1.4719

SiMe3 117.881 121.115 120.224 119.443 1.4734

PH2(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 1.4454

SH(c) 117.723 121.149 120.348 119.283 1.4681

Cl 118.038 120.982 120.273 119.452 1.4693

ClO3 118.761 120.572 120.109 119.877 1.4643

Br 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 ΔqAB

H 0.009 0.011 0.002

Li 0.033 0.024 0.009

BH2(c) 0.102 0.069 0.171

BH2(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 0.071

Me 0.008 0.006 0.014

CF3 0.007 0.044 0.037

Ph(c) 0.004 0.004 0.000

Ph(o) 0.005 0.006 0.001

CHO(c) 0.056 0.058 0.114

COMe(c) 0.049 0.051 0.100

COCl(c) 0.053 0.077 0.130

COO(c) 0.054 0.057 0.003

COO(o) 0.003 0.097 0.094

COOH(c) 0.039 0.054 0.093

COOMe(c) 0.037 0.047 0.084

CCH 0.005 0.020 0.015

CN 0.002 0.049 0.047

NH(c) 0.211 0.357 0.568

NH2(c) 0.126 0.069 0.195

NH2(p) 0.013 0.001 0.012

NF2(p) 0.012 0.053 0.065

 NH3 0.104 0.118 0.014

NO2(c) 0.027 0.071 0.098

NO2(o) 0.053 0.030 0.023

NC 0.026 0.027 0.001

 N2 0.008 0.304 0.312

O 0.135 0.303 0.438

OH(c) 0.094 0.036 0.130

OMe(c) 0.106 0.039 0.145

 OH2 (p) 0.118 0.129 0.011

F 0.067 0.008 0.075

Na 0.036 0.033 0.003

MgCl 0.006 0.016 0.010

SiH3 0.005 0.024 0.019

SiMe3 0.001 0.015 0.016

PH2(p) 0.015 0.022 0.007

 PH3 (a) 0.091 0.176 0.085

S 0.152 0.212 0.364

SH(c) 0.110 0.016 0.126

Cl 0.081 0.006 0.075

ClO3 0.061 0.064 0.003

Br 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 P

BCO SF 0.8151 0.8109 194.01 <0.0001

BCO SF , SR 0.9429 0.9403 355.08 <0.0001

BCO SF , SR, SE 0.9776 0.9760 611.72 <0.0001

BCO BCO 2 SF , SR, SE, (SF ) 0.9929 0.9922 1429.81 <0.0001

BCO 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 biphenyls

BIPH(c) BIPH(c) BIPH(c) Substituent ΔqA ΔqB ΔqAB

NH(c) 0.309 0.233 0.542

Br 0.051 0.004 0.055

π-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.