| FAIR Data table S1.a Free energies for dimerisation reactions of X+-CC−. | |||||||
|---|---|---|---|---|---|---|---|
| System | ΔG Reactant as ylidb |
ΔΔG reactant with free C2c |
1,1-substitution | 1,2-substitution | |||
| ΔG‡ d | ΔΔG‡ e | ΔG‡ d | ΔΔG‡ e,()h | ||||
| Pyridinium-CC | -648.57217 | 83.7 | -648.524263 | 30.1 | -648.526431 | 27.9(55.8) | |
| Me3P-CC | -1074.304518 | 117.6 | -1074.231749 | 45.7 | -1074.249573 | 34.5(83.1) | |
| Me2O-CC | -461.963546 | 42.3 | -461.925740 | 23.7 | -461.924414 | 24.6 (15.1) | |
| Me2S-CC | -1108.077286 | 79.6 | -1108.022629 -1108.072244f,-1108.064236g |
34.3 3.2, 8.2 | -1108.033959 -1108.115085f | 27.2 (52.4) -23.7f |
|
| Dibenzothiophenium-CC | -1872.442518 | 64.0 | -1872.390305 | 32.8 | -1872.399602 | 26.9(37.1) | |
| Me2S-CC + OPh | -860.817003 | 79.6 | -860.773300 | 27.4 | -860.778169 | 24.3(55.3) | |
| Me2Se-CC | -5114.8998 | 77.1 | -5114.846938 | 33.2 | -5114.855078 | 28.1(49.1) | |
| Me2Te-CC | -847.881032 | 82.7 | -847.824638 | 35.4 | -847.838789 | 26.5(56.2) | |
| MeF-CC | -431.342838 | -2.4 | -431.322316 | 12.9 | -431.319081 | 14.9(-17.3) | |
| MeCl-CC | -1152.180092 | 32.1 | -1152.143950 | 22.7 | -1152.146646 | 21.0(11.1) | |
| MeBr-CC | -5380.20545 | 35.6 | -5380.170459 | 22.0 | -5380.174492 | 19.4(16.2) | |
| MeI-CC | -827.38005 | 46.0 | -827.340998 | 24.5 | -827.345930 | 21.4(24.6) | |
| MeF2I-CC | -1226.714644 | 36.3 | -1226.682353 | 20.3 | -1226.694673 | 12.5(23.8) | |
| MeF2I-CC + OPh | -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. bΔG298 for two molecules of reactant. cΔΔG for dissociation of C2 from one molecule of reactant; ΔG for C2 = -75.879882 Hartree and corrected by -28.0 kcal/mol for estimated error in the calculated ΔG for C2. dΔG298 transition state energies in Hartree for TS1, the addition step; for a standard state of 0.044M (1 atm). 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 TS2. gΔG298 transition state energies in Hartree for TS3. hDifference in energy between the dimerisation TS1 and dissociated reactant with free C2, kcal/mol. | |||||||