| FAIR Data Table 1.a Free energies for reactions of 2. | |||||||
|---|---|---|---|---|---|---|---|
| 2, X= | ΔG298b | ΔΔG(3+X)-2c | TS 1,1-substitution | TS 1,2-substitution | |||
| ΔG‡TS1,1d | ΔΔG‡TS1,1e | ΔG‡TS1,2d | ΔΔG‡TS1,2e | ΔΔG, Unimolecular vs Bimolecularh |
|||
| 2Pyridinium | -648.572170 | 83.7 | -648.524263 | 30.1 | -648.526431 | 27.9 | 55.8 |
| Pyridinium + 6i | -631.064445 | 83.7 | -631.026556 | 23.8 | -631.024907 | 24.8 | 59.9 |
| Pyridinium + 7j | -864.847012 | 83.7 | -864.770770 | 47.8 | -864.802515 | 27.9 | 55.8 |
| 2Me3P | -1074.304518 | 117.6 | -1074.231749 | 45.7 | -1074.249573 | 34.5 | 83.1 |
| 2Me2O | -461.963546 | 42.3 | -461.925740 | 23.7 | -461.924414 | 24.6 | 18.6 |
| 2Me2S | -1108.077286 | 79.6 | -1108.022629 -1108.072244,f-1108.064236g |
34.3 3.2, 8.2 | -1108.033959 -1108.115085f | 27.2 -23.7f |
52.4 |
| Me2S + 6i | -860.817003 | 79.6 | -860.773300 | 27.4 | -860.778169 | 24.4 | 55.2 |
| Me2S + 7j | -1094.594027 | 79.6 | -1094.521364 | 45.6 | -1094.549341 | 28.0 | 51.6 |
| 2Dibenzothiophenium | -1872.442518 | 64.0 | -1872.390305 | 32.8 | -1872.399602 | 26.9 | 37.1 |
| Dibenzothiophenium + 6i | -1242.999619 | 64.0 | -1242.955887 | 27.4 | -1242.959748 | 25.0 | 25.0 |
| 2Me2Se | -5114.899800 | 77.1 | -5114.846938 | 33.2 | -5114.855078 | 28.1 | 49.1 |
| 2Me2Te | -847.881032 | 82.7 | -847.824638 | 35.4 | -847.838789 | 26.5 | 56.2 |
| 2MeF | -431.342838 | -2.4 | -431.322316 | 12.9 | -431.319081 | 14.9 | -15.3 |
| 2MeCl | -1152.180092 | 32.1 | -1152.143950 | 22.7 | -1152.146646 | 21.0 | 11.1 |
| 2MeBr | -5380.20545 | 35.6 | -5380.170459 | 22.0 | -5380.174492 | 19.4 | 16.2 |
| 2MeI | -827.380154 | 46.0 | -827.340998 | 24.5 | -827.345930 | 21.4 | 24.6 |
| 2PhI | -1210.7384 | 43.6 | -1210.701586 | 23.1 | -1210.707251 | 19.6 | 24.6 | PhI + 6e | -912.138973 | 43.6 | -912.107762 | 19.6 | -912.107781 | 19.6 | 24.6 |
| 2MeF2I | -1226.714644 | 36.3 | -1226.682353 | 20.3 | -1226.694673 | 12.5 | 23.8 |
| MeF2I + 6i | -920.135682 | 36.3 | -920.093724 | 26.3 | -920.098661 | 23.2 | 13.1 |
| aCalculations at the ωB97XD/Def2-TZVPPD/SCRF=dichloromethane level, data repository collection DOI: 10.14469/hpc/8168 for full details of calculation. This table has DOI: 10.14469/hpc/8280. bΔG298 for two molecules of reactant 2. Link to ΔG‡ loads data repository entry for this species. cΔΔG for the reaction 2 →(3+X). ΔG for C2 = -75.879882 Hartree, corrected by -28.0 kcal/mol for estimated error in the calculated ΔG for C2 at this level. dΔG298 transition state energies in Hartree for TS1, the addition step; for a standard state of 0.044M (1 atm). Link to ΔG‡ loads the data repository entry for this species. eΔΔG298‡ activation energies in kcal mol-1 Link to ΔΔG‡ loads a 3D model of the system and transition state normal mode animation. fΔG298 transition state energies in Hartree for a second transition state after intermediate formed from first transition state. gΔG298 transition state energies in Hartree for second transition state after intermediate formed from first transition state. hΔΔG(kcal mol-1) for unimolecular fragmentation of ΔG(3+X)-2) - ΔGTS1,1 or ΔGTS1,2. i6 = phenoxyl radical j7 = dihydroanthracene | |||||||