Table 1. Selected bond lengths, forward reaction barriers, and overall reaction energies from density functional theory calculations for reactions {[(η6-bz)Ru(en)X]n+·H2O} → [TS] → {[(η6-bz)Ru(en)(H2O)]2+·X}.
| X | Ru-X/Ru-OH2 reactant, Å | Ru-X/Ru-OH2 TS, Å | Ru-X/Ru-OH2 product, Å | ΔE‡, kcal·mol-1 | ΔEreac, kcal·mol-1* |
|---|---|---|---|---|---|
| Cl | 2.47/3.94 | 3.28/2.99 | 4.10/2.20 | 17.0 | 2.5 |
| Br | 2.63/3.99 | 3.39/2.88 | 4.24/2.21 | 16.0 | 1.9 |
| I | 2.85/4.44 | 3.66/2.95 | 4.48/2.22 | 18.1 | 5.2 |
| N3 | 2.15/4.34 | 2.77/3.00 | 3.75/2.19 | 25.4 | 8.2 |
| pcp | 2.11/3.89 | 2.95/2.75 | 3.92/2.18 | 8.4 | 6.7 |
| dcp | 2.13/4.04 | 2.90/2.67 | 3.92/2.17 | 21.6 | 5.2 |
| dfp | 2.12/4.08 | 2.89/2.71 | 4.00/2.18 | 22.6 | 5.4 |
| py | 2.12/3.85 | 2.91/2.77 | 3.88/2.17 | 23.5 | 5.1 |
| pic | 2.12/3.73 | 2.84/2.72 | 3.88/2.17 | 22.6 | 3.9 |
TS, transition state.
*
ΔEreac values relative to reactant species at zero.