Table 8.
Second order perturbation theory analysis of Fock matrix in NBO basis of compound 3.
| Donor NBO (i) | Acceptor NBO (j) | E(2)a (kJ/mol) | E(j) − E(i)b (a.u.) | F(i,j)c (a.u.) |
|---|---|---|---|---|
| π (C1-S3) | π* (C2-N15) | 24.6856 | 1.08 | 0.071 |
| π* (C4-C6) | 13.09592 | 1.2 | 0.055 | |
| σ (C1-C4) | π* (C1-N18) | 9.95792 | 1.26 | 0.049 |
| π* (C4-C5) | 9.99976 | 1.25 | 0.049 | |
| π* (C4-C6) | 8.5772 | 1.25 | 0.045 | |
| π (C1-N18) | σ* (C1-C4) | 9.70688 | 1.36 | 0.05 |
| π* (C2-N19) | 41.67264 | 0.31 | 0.054 | |
| π* (C4-C5) | 38.11624 | 0.35 | 0.055 | |
| π (C2-S3) | σ* (C1-C4) | 17.82384 | 1.14 | 0.062 |
| π (C2-N19) | π* (C1-N18) | 58.32496 | 0.33 | 0.064 |
| π (C4-C5) | π* (C4-C6) | 13.84904 | 1.26 | 0.058 |
| σ* (C5-H8) | 4.3932 | 1.16 | 0.031 | |
| π* (C6-C9) | 78.91024 | 0.29 | 0.067 | |
| π* (C7-C11) | 88.74264 | 0.27 | 0.068 | |
| π (C4-C6) | σ* (C1-C4) | 10.20896 | 1.16 | 0.048 |
| σ* (C6-H10) | 4.184 | 1.18 | 0.031 | |
| π (C5-C7) | π* (C4-C5) | 10.96208 | 1.26 | 0.051 |
| σ* (C5-H8) | 4.76976 | 1.17 | 0.033 | |
| σ* (C7-H12) | 4.89528 | 1.17 | 0.033 | |
| σ* (C11 -Cl14) | 19.91584 | 0.85 | 0.057 | |
| σ (C5-H8) | π* (C7-C11) | 14.81136 | 1.08 | 0.055 |
| π (C6-C9) | π* (C4-C6) | 9.91608 | 1.25 | 0.049 |
| σ* (C6-H10) | 4.85344 | 1.19 | 0.033 | |
| σ* (C9-H13) | 4.93712 | 1.17 | 0.033 | |
| σ* (C11-Cl14) | 19.83216 | 0.85 | 0.057 | |
| π (C7-C11) | π* (C5-C7) | 9.28848 | 1.3 | 0.048 |
| σ* (C7-H12) | 5.23 | 1.19 | 0.035 | |
| π (C9-C11) | π* (C6-C9) | 9.07928 | 1.3 | 0.048 |
| σ* (C9-H13) | 5.0208 | 1.19 | 0.034 | |
| σ (C11 -Cl14) | π* (C5-C7) | 9.79056 | 1.28 | 0.049 |
| π* (C6-C9) | 9.45584 | 1.29 | 0.048 | |
| LP(1) S3 | π* (C1-N18) | 8.5772 | 1.25 | 0.045 |
| π* (C2-N19) | 11.04576 | 1.23 | 0.051 | |
| LP(2) S3 | π* (C1-N18) | 97.9056 | 0.26 | 0.07 |
| π* (C2-N19) | 114.72528 | 0.25 | 0.075 | |
| LP(1)Cl14 | π* (C7-C11) | 6.6944 | 1.47 | 0.043 |
| π* (C9-C11) | 6.6944 | 1.47 | 0.044 | |
| LP(2)Cl14 | π* (C7-C11) | 16.5268 | 0.87 | 0.052 |
| π* (C9 – C11) | 16.5268 | 0.86 | 0.052 | |
| LP(3)Cl14 | π* (C7-C11) | 51.54688 | 0.32 | 0.061 |
| LP(1)N15 | π* (C2 – N19) | 156.64896 | 0.29 | 0.099 |
| LP(1)N18 | π* (C1-S3) | 69.07784 | 0.54 | 0.085 |
| σ* (C1-C4) | 4.93712 | 0.85 | 0.029 | |
| π* (C2 – N19) | 21.17104 | 0.92 | 0.062 | |
| σ* (C6-H10) | 2.3012 | 0.86 | 0.02 | |
| LP(1)N19 | π* (C1-N18) | 21.58944 | 0.95 | 0.064 |
| π* (C2-S3) | 65.35408 | 0.56 | 0.084 | |
| π* (C2-N15) | 7.7404 | 0.82 | 0.035 | |
| σ* (N15-H16) | 3.51456 | 0.83 | 0.024 |
aE(2) means energy of hyper conjugative interactions (stabilization energy in kJ/mol).
bEj − Ei is energy difference between donor and acceptor i and j NBO orbitals.
cF(i,j) is the Fock matrix element between i and j NBO orbitals.