Table 1 Comparison of the peri-selectivity of the reactions of Ir, Rh and Co: activation barriers and reaction energies for the first step of the various reactions of the Ir, Rh and Co complexes with ethylene
Metal | MO2(CH2)(CH3) | Activation energy | Reaction energy | |||
|---|---|---|---|---|---|---|
Reaction path | Addition | B3LYP | MO6 | B3LYP | MO6 | |
Singlet PES | ||||||
 Ir | Ir1 Ir2 | [1 + 1] | 38.8 (39.40) | 18.96 (19.21) | −20.67 (−20.10) | −24.88 (−23.76) |
Ir1 Ir3 | [3 + 2]O,O | 15.82 (16.23) | 8.24 (8.88) | −42.50 (−41.28) | −49.65 (−48.19) | |
Ir1 Ir4 | [3 + 2]C,O | 0.68 (0.89) | 0.39 (0.52) | −35.85 (−33.94) | −38.84 (−36.66) | |
Ir1 Ir8 | [2 + 2]Ir=O | 24.66 (25.52) | 11.98 (12.29) | −20.87 (−19.16) | −25.09 (−24.84) | |
Ir1 Ir10 | [2 + 2]Ir=C | 0.84 (1.01) | 0.51 (0.72) | −18.89 (−18.20) | −21.43 (−20.97) | |
 Rh | Rh1 Rh2 | [1 + 1] | 7.59 (8.43) | 4.08 (4.76) | −21.90 (−21.34) | −23.56 (−23.11) |
Rh1 Rh8 | [2 + 2]Rh=O | 10.28 (10.97) | 5.99 (6.84) | −26.30 (−25.59) | −29.59 (−28.68) | |
Rh1 Rh9 | [1 + 2]O | 33.73 (34.08) | 15.54 (16.56) | −5.42 (−4.97) | −8.45 (−7.91) | |
 Co | Co1 Co2 | [1 + 1] | 7.19 (7.65) | 3.98 (4.02) | −43.23 (−41.41) | −47.24 (−23.11) |
Co1 Co9 | [1 + 2]O | 4.95 (5.85) | 2.49 (2.84) | −43.35 (−42.06) | −48.05 (−28.68) | |
Doublet PES | ||||||
 Ir | Ir1 Ir2 | [1 + 1] | 20.27 (20.96) | 11.12 (10.98) | −12.86 (−12.23) | −15.43 (−14.79) |
Ir1 Ir3 | [3 + 2]O,O | 26.67 (27.21) | 12.89 (13.27) | −40.58 (−38.91) | −46.65 (−45.76) | |
Ir1 Ir4 | [3 + 2]C,O | 8.81 (9.14) | 4.21 (4.89) | −52.40 (−51.08) | −55.80 (−54.68) | |
Ir1 Ir8 | [2Â +Â 2]Ir=O | 30.49 (30.87) | 16.38 (17.12) | 9.43 (9.89) | 7.61 (7.89) | |
 Rh | Rh1 Rh2 | [1 + 1] | 13.79 (14.08) | 7.12 (7.59) | −14.65 (−14.01) | −18.42 (−17.92) |
Rh1 Rh4 | [3 + 2]C,O | 3.17 (4.02) | 2.04 (2.88) | −75.54 (−73.78) | −80.60 (−78.85) | |
Rh1 Rh8 | [2 + 2]Rh=O | 25.92 (27.45) | 13.78 (14.41) | −8.87 (−7.97) | −11.26 (−10.05) | |
Rh1 Rh9 | [1 + 2]O | 14.49 (14.89) | 6.92 (7.78) | −0.004 (0.07) | −0.02 (0.04) | |
 Co | Co1 Co2 | [1 + 1] | 37.16 (38.32) | 16.48 (17.05) | −80.50 (−79.84) | −89.12 (−88.63) |
Co1 Co3 | [3 + 2]O,O | 12.54 (13.02) | 7.76 (7.39) | −56.40 (−54.98) | −58.96 (−58.01) | |
Co1 Co4 | [3 + 2]O,C | 0.98 (1.25) | 0.56 (0.87) | −4.82 (−19.38) | −6.98 (−5.77) | |
Triplet PES | ||||||
 Ir | Ir1 Ir2 | [1 + 1] | 14.61 (15.24) | 7.77 (8.22) | −17.09 (−16.94) | −20.32 (−20.21) |
Ir1 Ir5 | [3 + 2]O,O | 4.91 (5.61) | 2.85 (3.45) | −18.84 (−18.08) | −22.41 (−21.97) | |
 Rh | Rh1 Rh2 | [1 + 1] | 12.53 (12.94) | 7.26 (7.99) | −14.56 (−14.04) | −17.47 (−18.21) |
Rh1 Rh5 | [1 + 1] | 1.98 (2.05) | 1.02 (1.54) | −25.39 (−24.47) | −28.82 (−28.22) | |
Rh1 Rh10 | [2 + 2]Rh=C | 11.98 (12.23) | 6.31 (6.79) | −19.89 (−19.38) | −22.18 (−21.78) | |
 Co | Co1 Co2 | [1 + 1] | 10.52 (10.87) | 5.34 (5.98) | −5.72 (−4.47) | −7.72 (−7.13) |
Co1 Co3 | [3 + 2]O,O | 1.05 (1.76) | 0.68 (0.89) | −46.80 (−46.14) | −52.89 (−51.52) | |