Aliphatic Carbon−Carbon Bond Activation of Nitriles by Rhodium(II) Porphyrin

Abstract

The aliphatic C(α)−C(β) bonds of a series of nitriles were activated by Rh(tmp) using Ph 3 P as the promoting ligand from 100 to 130 °C. Kinetic studies at 130 °C revealed the rate law, rate = k ‘ K 1 [Rh(tmp)][Ph 3 P] n + k 3 K 2 ( K 1 [Ph 3 P])/ (1 + K 1 [Ph 3 P])[Rh(tmp)][ t BuCN] and suggested the carbon−carbon bond activation occurred at the coordinated t BuCN with Rh(tmp) in a 1:1 ratio in the transition state.