Table 2. Bonding Analysis (EDA) of 3 and TS with and without N(CH3)3a.
| bonding analysis (EDA) | 3 | TS | TS + N(CH3)3 | |||
|---|---|---|---|---|---|---|
| ΔEint | –308 | –152 | –193 | |||
| ΔEint(disp)b | –12 | 4% | –13 | 9% | –21 | 11% |
| ΔEint(elec)b | –296 | 96% | –138 | 91% | –172 | 89% |
| ΔEPauli | 1742 | 852 | 957 | |||
| ΔEelstatc | –885 | 43% | –479 | 48% | –560 | 50% |
| ΔEorbc | –1153 | 57% | –511 | 52% | –569 | 50% |
| ΔEorb(S–N)d | –971 | 84% | –402 | 79% | –466 | 82% |
| ΔEorb(NH--F)d | –55 | 11% | –34 | 6% | ||
| ΔEorb(rest)d | –182 | 16% | –54 | 11% | –69 | 12% |
| ΔEprep | 15 | 260 | 266 | |||
| ΔEbond | –293 | 108 | 72 | |||
a
All energies in kJ/mol at PBE/TZ2P. Fragments for 3 are generated from homolytic cleavage at N–S into neutral doublets. For the TS, the reactants are used as fragments in a neutral, singlet configuration.
b
Percentage values: Relative contributions of dispersion and electronic effects to the interaction energy ΔEint.
c
Percentage values: Relative contributions between the attractive EDA terms ΔEelstat and ΔEorb.
d
Percentage values: Relative contributions to the orbital interaction ΔEorb. The character of the orbital contribution as S–N bond or NH--F hydrogen bond is revealed by NOCV analysis, as shown below. Non-assignable contributions are summed in the “rest” term.