Table 2. ΔTSG° (eq 4) and Δ+1G° (eq 10) for the Methyl Transfer from the Neutral nSAM+ Molecule to Various Nucleophiles Obtained from SMD Calculations with and without an Explicit H2O Moleculea.
| X–b | envb | ΔTSG° | envb | ΔTSG° | ΔDSG° | Δ+1Gwat° | Δ+1Geth° |
|---|---|---|---|---|---|---|---|
| Cl– | water | 104.1 | ether | 95.8 | –8.3 | ||
| Br– | 88.2 | 82.2 | –5.9 | ||||
| NCO– | 138.1 | 132.5 | –5.6 | ||||
| OCN– | 106.6 | 94.2 | –12.4 | ||||
| NCS– | 105.4 | 106.4 | 1.0 | ||||
| SCN– | 112.7 | 101.9 | –10.8 | ||||
| Cl– | water + 1c | 109.5 | ether + 1c | 99.6 | –9.9 | 5.4 | 3.8 |
| Br– | 94 | 94.4 | 0.4 | 5.8 | 12.2 | ||
| NCO– | 145.8 | 136.3 | –9.6 | 7.8 | 3.8 | ||
| NCO– | 142.7 | 139.6 | –3.1 | 4.6 | 7.2 | ||
| OCN– | 104 | 87.8 | –16.2 | –2.6 | –6.4 | ||
| OCN– | 111.4 | 97.7 | –13.7 | 4.8 | 3.4 | ||
| NCS– | 111.3 | 114.4 | 3.0 | 5.9 | 7.9 | ||
| NCS– | 112.5 | 103.6 | –8.8 | 7.1 | –2.8 | ||
| SCN– | 112.8 | 109.3 | –3.5 | 0.1 | 7.4 | ||
| SCN– | 113.3 | 106.4 | –7.0 | 0.6 | 4.4 |
a
All energies in kJ mol–1.
b
env, Chemical environment; X–, nucleophile.
c
One explicit H2O molecule included. The atom connecting to the H2O molecule is marked in bold-italic text.