Table 1.
Electronic energies[a] of stationary points relative to separate reactants (in kcal mol−1) for the oxidative addition of arylic (C6H5X)[b] and aliphatic (CH3X)[c] C–H, C–Cl, and C–C bonds to various model catalysts.
| C–X bond | Model catalyst | RC | TS | PC | |||
|---|---|---|---|---|---|---|---|
| C6H5X | (CH3X) | C6H5X | (CH3X) | C6H5X | (CH3X) | ||
| C–H | Pd | −21.7 | (−6.7) | −1.6 | (4.0) | −6.0 | (−3.6) |
| Pd(PH3) | −14.9 | (−7.7) | 17.1 | (15.7) | 16.9 | (14.9) | |
| Pd(PH3)2 | −0.4 | (0.0) | 27.4 | (32.6) | 24.2 | (27.3) | |
| Pd(PH2C2H4PH2) | −7.7 | (−1.3) | 13.6 | (18.6) | 10.0 | (12.6) | |
| C–Cl | Pd | −19.2 | (−12.9) | −8.1 | (−0.6) | −33.8 | (−33.5) |
| Pd(PH3) | −14.4 | (−12.9) | −4.4 | (2.3) | −23.8 | (−26.9) | |
| Pd(PH3)2 | −0.4 | (−0.5) | 19.2 | (27.1) | −9.6 | (−11.6) | |
| Pd(PH2C2H4PH2) | −8.8 | (−6.4) | 5.5 | (14.3) | −24.9 | (−27.1) | |
| C–C | Pd | −19.7 | (−6.7) | 11.0 | (18.5) | −8.5 | (−9.4) |
| Pd(PH3) | −15.1 | (−7.9) | 22.8 | (26.3) | 14.6 | (13.6) | |
| Pd(PH3)2 | −0.3 | (0.0) | 45.7 | (51.7) | 27.1 | (26.6) | |
| Pd(PH2C2H4PH2) | −5.3 | (−1.7) | 33.7 | (38.4) | 12.0 | (11.3) | |