| FAIR Data Table S2. Computed energies for model systems as a system calibration | ||||||||
|---|---|---|---|---|---|---|---|---|
| Method/Basis set | 1a | 2a | 3a | 4b | 5a | 6a | 7c | 8d |
| MeI + CCIMe | ΔE−CC-I+Me | ΔECC | ΔEMeI | ΔΔE1-(2+3) | ΔG2+2x3 | ΔE‡1,2-TS | ΔΔE6-5 | ΔΔE‡6-(1+3) |
| CCSD(T)/Def2-TZVPPD | -412.849513 | -75.786329 | -336.981137 | -51.5 | -749.748602 | -749.788507 | -25.0 (-29.6)e | 6.4 |
| CCSD(T)/Def2-SVPD | -412.293874 | -75.6658365 | -336.559022 | -43.3 | -748.783881 | -748.811968 | -17.6 ()-22.2)e | 25.7 |
| ωB97XD/Def2-TZVPPD | -413.702954 | -75.8658745 | -337.704325 | -83.3 | -751.274524 | -751.361189 (-751.36144)f | -54.4 | 29.0/28.9f |
| ωB97XD/Def2-SVPD | -413.557258 | -75.7780175 | -337.646958 | -83.0 | -751.071934 | -751.162964 | -57.1 | 25.9 |
| B3LYP+GD3BJ/Def2-TZVPPD | -413.779992 | -75.911830 | -337.742767 | -78.7 | -751.397366 | -751.484990 | -55.0 | 23.7 |
| M062X/Def2-TZVPPD | -413.535520 | -75.874608 | -337.534656 | -79.2 | -750.943920 | -751.026295 | -51.7 | 27.5 |
| B2PLY3D3/Def2-TZVPPD | -413.086470 | -75.7353341 | -337.217631 | -83.8 | -750.170596 | -750.257453 | -54.5 | 29.3 |
| PBEQIDH/Def2-TZVPPD | -412.993046 | -75.6582135 | -337.190534 | -90.5 | -750.039282 | -750.133650 | -59.2 | 31.3 |
| MeI + CCIMe | ΔG−CC-I+Me | ΔGCC | ΔGMeI | ΔΔG1-(2+3) | ΔG2+2x3 | ΔG‡1,2-TS | ΔΔG6-5 | ΔΔG‡6-(1+3) |
| CCSD(T)/Def2-TZVPPD | -412.837278 | -75.800442 | -336.969115 | -42.5 | -749.738672 | -749.746951f | -5.2 (-9.8)e,f | 37.3/35.4f,g |
| CCSD(T)/Def2-SVPD | -412.282092 | -75.679918 | -336.547139 | -34.5 | -748.774196 | -748.770828 | +0.2 (-4.6)e,f | 36.6/34.7g |
| ωB97XD/Def2-TZVPPD | -413.690020 | -75.879884 | -337.692199 | -74.0 | -751.264282 | -751.320309 (-751.323261)f | -35.2 | 38.8/36.9f |
| ωB97XD/Def2-SVPD | -413.544884 | -75.791993 | -337.635095 | -73.9 | -751.062183 | -751.122380 (-751.126099)f | -37.8 | 36.1/33.8f |
| B3LYP+GD3BJ/Def2-TZVPPD | -413.767624 | -75.925885 | -337.730995 | -69.5 | -751.387875 | -751.444497 | -35.5 | 34.0 |
| M062X/Def2-TZVPPD | -413.522416 | -75.888581 | -337.522434 | -69.0 | -750.933449 | -750.988334 | -34.4 | 45.5 |
| B2PLYPD3/Def2-TZVPPD | -413.393110 | -75.883353 | -337.420658 | -55.9 | -750.724669 | -750.756287 | -19.8 | 36.0 |
| PBEQIDH/Def2-TZVPPD | -413.346512 | -75.816702 | -337.428873 | -63.3 | -750.674448 | -750.720129 | -28.7 | 34.7 |
| MeO• + CCIMe | ΔG−CC-I+Me | ΔGCC | ΔGMeI | ΔGPhO | ΔG-CCI++PhO | ΔG‡1,2-TS | ΔΔG6-(2+3+4) | ΔΔG‡6-5 |
| ωB97XD/Def2-TZVPPD | -413.690020 | -75.879884 | -337.692199 | -306.778361 | -720.462035 | -720.428314 | -48.9 | 21.1 |
| aEnergies in Hartree. bEnergy of free C2 and MeI compared to bound precursor. cEnergy (kcal/mol) of the transition state for 1,2-substitution compared to that of the reactant as free C2. dTransition state barrier (kcal/mol) for the 1,2-substitution reaction. eCorrected for the error inferred for the CCSD(T)/Def2-TZVPPD method calibrated using the experimental dissociation energies of HCCH to HCC + H and to CC + 2H. fThermal and entropic contributions estimated from those obtained at the CCSD(T)/Def2-SVPD level. gEnergy for the reduced symmetry C2 species compared to C2h symmetry. | ||||||||