The aliphatic C(α)−C(β) bonds of a series of nitrileswere activated by Rh(tmp) using Ph3P as the promoting ligandfrom 100 to 130 °C. Kinetic studies at 130 °C revealed therate law, rate = k‘K1[Rh(tmp)][Ph3P]n + k3K2(K1[Ph3P])/(1 + K1[Ph3P])[Rh(tmp)][tBuCN] and suggested the carbon−carbon bond activation occurred at the coordinated tBuCNwith Rh(tmp) in a 1:1 ratio in the transition state.
The aliphatic C(α)−C(β) bonds of a series of nitriles were activated by Rh(tmp) using PPh3 as the promoting ligand. Kinetic studies at 130 °C revealed the activation followed the rate law, rate = −d[Rh(tmp)]/dt = k‘K1[Rh(tmp)]0[Ph3P]n + k3K2(K1[Ph3P])/(1 + K1[Ph3P])[Rh(tmp)]0[tBuCN].