Substituent effecton the geometricand electronic structure ofbenzenesulfonicacid:gas-phase electron diffraction andquantum chemical study of 4-CH3C6H4SO3H and 3-NO2C6H4SO3H molecules
Nina I. Giricheva • Georgiy V. Girichev • Michail S. Fedorov• Sergey N. Ivanov
SUPPLEMENTARY MATERIAL
Table S1 Experimental interatomic distances, experimental and calculated vibrational amplitudes and vibrational corrections for conformer I of 3-NBSA. Non-bonded distances involving hydrogen atoms are not included
Parameter / r / lexp. / lcalc. / r=rh1-ra / № groupO1-H1 / 0.964 / 0.047(5) / 0.069 / 0.0049 / 1
C2-H2 / 1.084 / 0.053(5) / 0.074 / 0.0052 / 1
O4-N1 / 1.222 / 0.039(1) / 0.039 / 0.0012 / 2
O5-N1 / 1.223 / 0.039(1) / 0.039 / 0.0012 / 2
C2-C3 / 1.390 / 0.045(1) / 0.045 / 0.0017 / 2
C2-C1 / 1.391 / 0.046(1) / 0.045 / 0.0017 / 2
C4-C3 / 1.392 / 0.046(1) / 0.045 / 0.0015 / 2
C5-C4 / 1.394 / 0.045(1) / 0.045 / 0.0012 / 2
C6-C5 / 1.395 / 0.046(1) / 0.045 / 0.0012 / 2
C1-C6 / 1.396 / 0.046(1) / 0.046 / 0.0014 / 2
O3-S1 / 1.441 / 0.035(1) / 0.035 / 0.0008 / 2
O2-S1 / 1.433 / 0.036(1) / 0.036 / 0.0009 / 2
N1-C3 / 1.474 / 0.053(1) / 0.053 / 0.0019 / 2
O1-S1 / 1.618 / 0.048(1) / 0.048 / 0.0014 / 2
S1-C1 / 1.782 / 0.054(1) / 0.053 / 0.0016 / 2
O5-O4 / 2.163 / 0.047(2) / 0.049 / 0.0055 / 3
O5-C3 / 2.312 / 0.060(2) / 0.061 / 0.0033 / 3
O4-C3 / 2.310 / 0.060(2) / 0.061 / 0.0040 / 3
C1-C3 / 2.376 / 0.055(2) / 0.056 / 0.0065 / 3
C5-C3 / 2.396 / 0.055(2) / 0.056 / 0.0056 / 3
C1-C5 / 2.407 / 0.055(2) / 0.056 / 0.0053 / 3
C6-C4 / 2.413 / 0.055(2) / 0.056 / 0.0051 / 3
C2-C6 / 2.430 / 0.055(2) / 0.056 / 0.0050 / 3
C2-C4 / 2.435 / 0.054(2) / 0.056 / 0.0050 / 3
O3-O1 / 2.446 / 0.080(2) / 0.082 / 0.0055 / 3
N1-C2 / 2.463 / 0.064(2) / 0.066 / 0.0066 / 3
N1-C4 / 2.464 / 0.064(2) / 0.066 / 0.0065 / 3
O2-O1 / 2.456 / 0.071(2) / 0.073 / 0.0048 / 3
O3-O2 / 2.501 / 0.059(2) / 0.061 / 0.0042 / 3
O3-C1 / 2.631 / 0.077(2) / 0.078 / 0.0035 / 3
O2-C1 / 2.636 / 0.079(2) / 0.080 / 0.0041 / 3
O1-C1 / 2.634 / 0.095(2) / 0.097 / 0.0046 / 3
O4-C2 / 2.739 / 0.115(2) / 0.099 / 0.0199 / 4
O5-C4 / 2.741 / 0.115(2) / 0.099 / 0.0205 / 4
S1-C2 / 2.738 / 0.088(2) / 0.073 / 0.0077 / 4
S1-C6 / 2.743 / 0.088(2) / 0.073 / 0.0075 / 4
C6-C3 / 2.761 / 0.079(2) / 0.063 / 0.0078 / 4
C1-C4 / 2.776 / 0.080(2) / 0.064 / 0.0076 / 4
C2-C5 / 2.806 / 0.079(2) / 0.064 / 0.0067 / 4
O3-C6 / 3.001 / 0.174(2) / 0.159 / 0.0224 / 4
O2-C2 / 3.001 / 0.174(2) / 0.158 / 0.0237 / 4
O1-C6 / 3.407 / 0.279(3) / 0.254 / 0.0315 / 5
O1-C2 / 3.439 / 0.289(3) / 0.264 / 0.0373 / 5
O5-C2 / 3.529 / 0.093(3) / 0.069 / 0.0317 / 5
O4-C4 / 3.530 / 0.093(3) / 0.069 / 0.0325 / 5
N1-C1 / 3.721 / 0.094(3) / 0.067 / 0.0137 / 6
N1-C5 / 3.735 / 0.094(3) / 0.067 / 0.0129 / 6
O3-C2 / 3.820 / 0.135(3) / 0.108 / 0.0404 / 6
O2-C6 / 3.835 / 0.129(3) / 0.102 / 0.0422 / 6
S1-C3 / 4.012 / 0.098(3) / 0.072 / 0.0158 / 6
S1-C5 / 4.035 / 0.098(3) / 0.072 / 0.0147 / 6
O4-C1 / 4.112 / 0.126(3) / 0.100 / 0.0023 / 6
O5-C5 / 4.118 / 0.127(3) / 0.101 / 0.0039 / 6
N1-C6 / 4.229 / 0.097(3) / 0.071 / 0.0163 / 6
O3-C5 / 4.351 / 0.178(3) / 0.151 / 0.0059 / 6
O2-C3 / 4.349 / 0.177(3) / 0.151 / 0.0044 / 6
S1-C4 / 4.545 / 0.095(5) / 0.073 / 0.0186 / 7
O1-C5 / 4.651 / 0.252(5) / 0.229 / 0.0302 / 7
O1-C3 / 4.658 / 0.258(5) / 0.235 / 0.0349 / 7
O5-C1 / 4.660 / 0.098(5) / 0.075 / 0.0353 / 7
O4-C5 / 4.678 / 0.098(5) / 0.075 / 0.0357 / 7
O5-C6 / 4.910 / 0.104(3) / 0.090 / 0.0205 / 8
O4-C6 / 4.916 / 0.103(3) / 0.090 / 0.0215 / 8
O4-O2 / 5.060 / 0.280(3) / 0.266 / 0.0861 / 8
O3-C3 / 4.924 / 0.124(3) / 0.111 / 0.0423 / 8
O2-C5 / 4.967 / 0.121(3) / 0.107 / 0.0442 / 8
O1-C4 / 5.181 / 0.190(3) / 0.176 / 0.0281 / 8
O3-C4 / 5.164 / 0.137(3) / 0.124 / 0.0226 / 8
N1-S1 / 5.186 / 0.107(3) / 0.093 / 0.0244 / 8
O2-C4 / 5.184 / 0.138(3) / 0.124 / 0.0248 / 8
O2-N1 / 5.235 / 0.214(3) / 0.201 / 0.0147 / 8
O4-S1 / 5.282 / 0.156(3) / 0.142 / 0.0094 / 8
O1-N1 / 5.755 / 0.353(3) / 0.340 / 0.0568 / 8
O4-O1 / 5.778 / 0.474(3) / 0.460 / 0.0445 / 8
O3-N1 / 6.208 / 0.155(4) / 0.138 / 0.0679 / 9
O5-S1 / 6.230 / 0.110(4) / 0.092 / 0.0616 / 9
O5-O2 / 6.354 / 0.219(4) / 0.202 / 0.0421 / 9
O4-O3 / 6.430 / 0.204(4) / 0.186 / 0.0592 / 9
O5-O1 / 6.794 / 0.344(4) / 0.326 / 0.0896 / 9
O5-O3 / 7.166 / 0.166(16) / 0.148 / 0.0943 / 10
All values are in Å. Least-squares standard deviations are given in parentheses as units in the last digit
Table S2 Experimental interatomic distances, experimental and calculated vibrational amplitudes and vibrational corrections for conformer IIof 3-NBSA. Non-bonded distances involving hydrogen atoms are not included
Parameter / r / lexp. / lcalc. / r=rh1-ra / № groupO1-H1 / 0.963 / 0.049(5) / 0.071 / 0.0052 / 1
C2-H2 / 1.084 / 0.053(5) / 0.074 / 0.0052 / 1
O4-N1 / 1.221 / 0.039(1) / 0.039 / 0.0012 / 2
O5-N1 / 1.223 / 0.039(1) / 0.039 / 0.0012 / 2
C2-C3 / 1.389 / 0.045(1) / 0.045 / 0.0018 / 2
C2-C1 / 1.393 / 0.046(1) / 0.045 / 0.0017 / 2
C4-C3 / 1.392 / 0.046(1) / 0.045 / 0.0016 / 2
C5-C4 / 1.393 / 0.045(1) / 0.045 / 0.0012 / 2
C6-C5 / 1.395 / 0.046(1) / 0.045 / 0.0012 / 2
C1-C6 / 1.398 / 0.046(1) / 0.046 / 0.0014 / 2
O2-S1 / 1.433 / 0.035(1) / 0.035 / 0.0008 / 2
O3-S1 / 1.442 / 0.036(1) / 0.036 / 0.0009 / 2
N1-C3 / 1.475 / 0.053(1) / 0.053 / 0.0019 / 2
O1-S1 / 1.618 / 0.048(1) / 0.048 / 0.0014 / 2
S1-C1 / 1.782 / 0.054(1) / 0.054 / 0.0016 / 2
O5-O4 / 2.162 / 0.047(2) / 0.049 / 0.0056 / 3
O5-C3 / 2.311 / 0.060(2) / 0.061 / 0.0032 / 3
O4-C3 / 2.310 / 0.060(2) / 0.061 / 0.0040 / 3
C1-C3 / 2.375 / 0.055(2) / 0.056 / 0.0066 / 3
C5-C3 / 2.396 / 0.055(2) / 0.056 / 0.0056 / 3
C1-C5 / 2.408 / 0.055(2) / 0.056 / 0.0053 / 3
C6-C4 / 2.413 / 0.055(2) / 0.056 / 0.0051 / 3
C2-C6 / 2.433 / 0.055(2) / 0.056 / 0.0050 / 3
C2-C4 / 2.436 / 0.054(2) / 0.056 / 0.0050 / 3
O2-O1 / 2.440 / 0.084(2) / 0.085 / 0.0060 / 3
N1-C2 / 2.462 / 0.064(2) / 0.066 / 0.0066 / 3
N1-C4 / 2.465 / 0.064(2) / 0.066 / 0.0065 / 3
O3-O1 / 2.462 / 0.071(2) / 0.073 / 0.0047 / 3
O3-O2 / 2.501 / 0.059(2) / 0.061 / 0.0042 / 3
O2-C1 / 2.627 / 0.078(2) / 0.079 / 0.0039 / 3
O3-C1 / 2.640 / 0.078(2) / 0.080 / 0.0035 / 3
O1-C1 / 2.634 / 0.097(2) / 0.098 / 0.0047 / 3
O4-C2 / 2.739 / 0.115(2) / 0.099 / -0.0204 / 4
O5-C4 / 2.739 / 0.115(2) / 0.099 / -0.0211 / 4
S1-C2 / 2.735 / 0.088(2) / 0.073 / 0.0077 / 4
S1-C6 / 2.747 / 0.088(2) / 0.072 / 0.0074 / 4
C6-C3 / 2.762 / 0.079(2) / 0.063 / 0.0078 / 4
C1-C4 / 2.776 / 0.080(2) / 0.064 / 0.0076 / 4
C2-C5 / 2.808 / 0.079(2) / 0.064 / 0.0067 / 4
O3-C6 / 3.003 / 0.169(2) / 0.154 / -0.0266 / 4
O2-C2 / 3.002 / 0.183(2) / 0.168 / -0.0199 / 4
O1-C2 / 3.376 / 0.278(3) / 0.253 / 0.0281 / 5
O1-C6 / 3.469 / 0.293(3) / 0.269 / 0.0413 / 5
O5-C2 / 3.528 / 0.093(3) / 0.069 / 0.0320 / 5
O4-C4 / 3.529 / 0.093(3) / 0.069 / 0.0329 / 5
N1-C1 / 3.720 / 0.094(3) / 0.067 / 0.0137 / 6
N1-C5 / 3.735 / 0.094(3) / 0.067 / 0.0129 / 6
O2-C6 / 3.811 / 0.141(3) / 0.115 / 0.0418 / 6
O4-H3 / 3.842 / 0.169(3) / 0.143 / 0.0531 / 6
O3-C2 / 3.842 / 0.124(3) / 0.097 / 0.0416 / 6
S1-C3 / 4.009 / 0.098(3) / 0.072 / 0.0158 / 6
S1-C5 / 4.037 / 0.098(3) / 0.071 / 0.0147 / 6
O4-C1 / 4.112 / 0.127(3) / 0.100 / -0.0028 / 6
O5-C5 / 4.116 / 0.127(3) / 0.101 / -0.0043 / 6
N1-C6 / 4.230 / 0.097(3) / 0.071 / 0.0163 / 6
O2-C3 / 4.342 / 0.182(3) / 0.156 / -0.0023 / 6
O3-C5 / 4.361 / 0.172(5) / 0.149 / -0.0087 / 7
S1-C4 / 4.545 / 0.096(5) / 0.073 / 0.0186 / 7
O1-C3 / 4.613 / 0.245(5) / 0.222 / 0.0275 / 7
O5-C1 / 4.659 / 0.097(5) / 0.075 / 0.0356 / 7
O1-C5 / 4.697 / 0.268(5) / 0.245 / 0.0377 / 7
O4-C5 / 4.678 / 0.098(5) / 0.076 / 0.0360 / 7
O5-C6 / 4.909 / 0.104(3) / 0.090 / 0.0205 / 8
O4-C6 / 4.918 / 0.104(3) / 0.090 / 0.0213 / 8
O4-O2 / 5.067 / 0.299(3) / 0.286 / -0.0791 / 8
O2-C5 / 4.941 / 0.130(3) / 0.116 / 0.0436 / 8
O3-C3 / 4.947 / 0.116(3) / 0.103 / 0.0433 / 8
O1-C4 / 5.181 / 0.192(3) / 0.178 / 0.0281 / 8
O2-C4 / 5.165 / 0.139(3) / 0.125 / 0.0251 / 8
N1-S1 / 5.183 / 0.107(3) / 0.093 / 0.0243 / 8
O3-C4 / 5.183 / 0.136(3) / 0.122 / 0.0221 / 8
O2-N1 / 5.234 / 0.226(3) / 0.212 / -0.0107 / 8
O4-S1 / 5.278 / 0.156(3) / 0.142 / -0.0105 / 8
O4-O1 / 5.676 / 0.467(3) / 0.453 / 0.0282 / 8
O1-N1 / 5.680 / 0.341(3) / 0.327 / 0.0455 / 8
O5-S1 / 6.227 / 0.110(4) / 0.092 / 0.0622 / 9
O3-N1 / 6.238 / 0.141(4) / 0.123 / 0.0700 / 9
O5-O2 / 6.349 / 0.228(4) / 0.210 / 0.0452 / 9
O4-O3 / 6.460 / 0.187(4) / 0.169 / 0.0609 / 9
O5-O1 / 6.727 / 0.334(4) / 0.317 / 0.0817 / 9
O5-O3 / 7.195 / 0.152(16) / 0.135 / 0.0970 / 10
All values are in Å. Least-squares standard deviations are given in parentheses as units in the last digit
Table S3 Experimental interatomic distances, experimental and calculated vibrational amplitudes and vibrational corrections for 4-MBSA. Non-bonded distances involving hydrogen atoms are not included
Parameter / r / lexp. / lcalc. / r=rh1-ra / № groupO1-H1 / 0.963 / 0.066(2) / 0.069 / 0.0050 / 1
C6-H7 / 1.092 / 0.072(2) / 0.075 / 0.0052 / 1
C1-H3 / 1.101 / 0.075(2) / 0.078 / 0.0056 / 1
C6-C5 / 1.397 / 0.048(1) / 0.045 / 0.0015 / 2
C1-C2 / 1.400 / 0.049(1) / 0.045 / 0.0013 / 2
C2-C3 / 1.398 / 0.049(1) / 0.045 / 0.0015 / 2
C1-C6 / 1.401 / 0.049(1) / 0.046 / 0.0013 / 2
C3-C4 / 1.406 / 0.049(1) / 0.046 / 0.0016 / 2
C4-C5 / 1.407 / 0.049(1) / 0.046 / 0.0016 / 2
O3-S1 / 1.427 / 0.039(1) / 0.035 / 0.0008 / 2
O2-S1 / 1.436 / 0.039(1) / 0.036 / 0.0009 / 2
C1-C4 / 1.515 / 0.054(1) / 0.050 / 0.0017 / 2
O1-S1 / 1.617 / 0.051(1) / 0.048 / 0.0014 / 2
S1-C1 / 1.764 / 0.056(1) / 0.053 / 0.0015 / 2
C1-C5 / 2.389 / 0.056(2) / 0.056 / 0.0054 / 3
C1-C3 / 2.405 / 0.056(2) / 0.056 / 0.0053 / 3
C3-C5 / 2.412 / 0.056(2) / 0.056 / 0.0050 / 3
C6-C2 / 2.449 / 0.056(2) / 0.056 / 0.0047 / 3
C2-C4 / 2.438 / 0.056(2) / 0.056 / 0.0056 / 3
O1-O3 / 2.423 / 0.081(2) / 0.081 / 0.0051 / 3
O1-O2 / 2.448 / 0.073(2) / 0.072 / 0.0043 / 3
C1-C5 / 2.539 / 0.069(2) / 0.069 / 0.0067 / 3
C1-C3 / 2.538 / 0.069(2) / 0.068 / 0.0066 / 3
O3-O2 / 2.495 / 0.060(2) / 0.060 / 0.0036 / 3
O3-C1 / 2.606 / 0.077(2) / 0.077 / 0.0044 / 3
O2-C1 / 2.618 / 0.078(2) / 0.078 / 0.0045 / 3
O1-C1 / 2.642 / 0.093(2) / 0.093 / 0.0056 / 3
S1-C6 / 2.709 / 0.071(3) / 0.071 / 0.0073 / 4
S1-C2 / 2.744 / 0.071(3) / 0.071 / 0.0072 / 4
C2-C5 / 2.788 / 0.063(3) / 0.063 / 0.0065 / 4
C6-C3 / 2.816 / 0.063(3) / 0.063 / 0.0064 / 4
C1-C4 / 2.791 / 0.063(3) / 0.063 / 0.0085 / 4
O2-C2 / 2.995 / 0.142(3) / 0.142 / 0.0203 / 4
O3-C6 / 2.971 / 0.156(3) / 0.156 / 0.0148 / 4
O1-C6 / 3.331 / 0.224(8) / 0.239 / 0.0274 / 5
O1-C2 / 3.494 / 0.225(8) / 0.240 / 0.0352 / 5
C1-C6 / 3.831 / 0.079(4) / 0.069 / 0.0140 / 6
C1-C2 / 3.822 / 0.078(4) / 0.068 / 0.0138 / 6
O3-C2 / 3.809 / 0.115(4) / 0.106 / 0.0362 / 6
O2-C6 / 3.834 / 0.101(4) / 0.091 / 0.0372 / 6
S1-C5 / 3.996 / 0.080(4) / 0.070 / 0.0147 / 6
S1-C3 / 4.030 / 0.079(4) / 0.070 / 0.0146 / 6
C1-C1 / 4.298 / 0.079(8) / 0.071 / 0.0181 / 7
O2-C3 / 4.370 / 0.149(8) / 0.141 / 0.0037 / 7
O3-C5 / 4.332 / 0.157(8) / 0.148 / 0.0002 / 7
S1-C4 / 4.546 / 0.079(8) / 0.071 / 0.0192 / 7
C6-H3 / 4.492 / 0.136(8) / 0.127 / 0.0749 / 7
O1-C5 / 4.553 / 0.225(8) / 0.217 / 0.0279 / 7
O1-C3 / 4.682 / 0.230(8) / 0.222 / 0.0346 / 7
O3-C3 / 4.941 / 0.103(5) / 0.109 / 0.0391 / 8
O2-C5 / 4.963 / 0.092(5) / 0.098 / 0.0395 / 8
O1-C4 / 5.141 / 0.166(5) / 0.172 / 0.0293 / 8
O3-C4 / 5.176 / 0.115(5) / 0.121 / 0.0254 / 8
O2-C4 / 5.212 / 0.111(5) / 0.117 / 0.0235 / 8
S1-C1 / 6.050 / 0.095(6) / 0.078 / 0.0322 / 9
O1-C1 / 6.583 / 0.200(8) / 0.200 / 0.0443 / 10
O3-C1 / 6.635 / 0.138(8) / 0.138 / 0.0406 / 10
O2-C1 / 6.680 / 0.132(8) / 0.131 / 0.0361 / 10
All values are in Å. Least-squares standard deviations are given in parentheses as units in the last digit
Table S4. The energetic contributions (kcal/mol) of the orbital interactions giving rise to inductive and mesomeric effects for methyl, sulfonyl, and nitro groups in mono- anddisubstituted benzenes
С6H5 –CH3 / С6H5 – SO3H / С6H5 – NO2 / 4-MBSA / 3-NBSA / 2-NBSACH3 / E(+I) / 18.2 / 10.0
E(-I) / -11.8 / -1.0
E(+C) / 6.7 / 7.2
E(-C) / -5.4 / -5.2
Е / 7.7 / 11.0
SO3H / E(+I) / 9.4 / 9.3 / 9.6 / 9.3
E(-I) / -9.7 / -9.7 / -9.0 / -7.5
E(+C) / 1.8 / 1.8 / 1.8 / 2.4
E(-C) / -7.0 / -7.8 / -6.9 / -6.1
Е / -5.5 / -6.4 / -4.5 / -1.9
NO2 / E(+I) / 8.8 / 9.1 / 7.9
E(-I) / -14.0 / -13.5 / -13.6
E(+C) / 3.0 / 4.1 / 2.7
E(-C) / -23.7 / -25.5 / -21.6
Е / -25.9 / -25.8 / -24.6
Fig. S1. Model of +I effect in 3-NBSA: transfer of electron density to a * orbital of the benzene ring. The interaction (c) involves the natural bonding orbital σ(C3–N) (a) and the natural antibonding orbital σ*(C1–C2) (b)
Fig. S2. a) Natural bonding orbital σ(C1–С2); b) natural antibonding orbital σ*(C3–N); c) result of the interaction between the two orbitals, modeling the –I effect in 3-NBSA
Fig. S3. Model of +C effect in 3-NBSA: transfer of electron density to a * orbital of the benzene ring. The interaction involves the natural bonding orbital π(O4-N) and the natural antibonding orbital π*(C3–C4)
Fig. S4 Model of C effect in 3-NBSA: transfer of electron density from a orbital of the benzene ring. The interaction involves the natural bonding orbital π(C3–C4) and the natural antibonding orbital π*(O4–N)
Table S5 The interacting donor and acceptor orbitals determining the electronic effects of the NO2 and SO3H substituents in 3-NBSA, their interaction energies E(2), and the energiesE(+I), E(-I), E(+C), E(-C), andЕ
donor / acceptor / E(2) a)Substituent NO2
The interacting donor and acceptor orbitals determining the inductive +I effect of the substituent
(N-O4) / *(C3-C4) / 1.0
(N-O5) / *(C2-C3) / 1.0
(N-C3) / *(C1-C2) / 2.1 (Fig. S1)
(N-C3) / *(C4-C5) / 1.9
LP(O5) / *(C2-C3) / 0.9
LP(O5) / *(C4-C5) / 0.7
LP(O4) / *(C1-C2) / 0.7
LP(O4) / *(C3-C4) / 0.8
E(+I) / 9.1
The interacting donor and acceptor orbitals determining the inductive -I effect of the substituent
(C2-C3) / *(N-O5) / 2.1
( C1-C2) / *( N-C3) / 4.5 (Fig. S2)
( C4-C5) / *( N-C3) / 4.8
(C3-C4) / *(N-O4) / 2.1
E(-I) / -13.5
The interacting donor and acceptor orbitals determining the mesomeric +C effect of the substituent
(N-O4) / *(C3-C4) / 4.1 (Fig. S3)
E(+C) / 4.1
The interacting donor and acceptor orbitals determining the mesomeric -C effect of the substituent
(C3-C4) / *(N-O4) / 25.5 (Fig. S4)
E(-C) / -25.5
Е / -25.8
Substituent SO3H
The interacting donor and acceptor orbitals determining the inductive +I effect of the substituent
(S-O3) / *(C1-C2) / 1.0
(S-O2) / *(C1-C6) / 1.0
(S-C1) / *(C2-C3) / 3.2
(S-C1) / *(C5-C6) / 3.1
LP(O3) / *(C1-C2) / 0.7
LP(O2) / *(C1-C6) / 0.6
E(+I) / 9.6
The interacting donor and acceptor orbitals determining the inductive -I effect of substituent
(C2-C3) / *(S-C1) / 4.3
(C1-C6) / *(S-O2) / 0.5
(C5-C6) / *(S-C1) / 4.2
E(-I) / -9.0
The interacting donor and acceptor orbitals determining the mesomeric +C effect of the substituent
(S-O1) / *(C1-C2) / 0.8
LP(O1) / *(C1-C2) / 1.0
E(+C) / 1.8
The interacting donor and acceptor orbitals determining the mesomeric -C effect of the substituent
(C1-C2) / *(S-O3) / 0.8
(C1-C2) / *(S-O2) / 0.6
(C1-C2) / *(S-O1) / 5.5
E(-C) / -6.9
Е / -4.5
a) threshold 0.5 kcal/mol