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Mechanistic Studies of Si−CN and C−NC Bond Activation of Silylnitriles and Alkyl Isonitriles by Rhodium Porphyrin Radical:  Novel Cyanide Transfer

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journal contribution
posted on 23.10.2006, 00:00 authored by Lirong Zhang, Chun Wah Fung, Kin Shing Chan
The Si−CN and C−NC bonds of silylnitriles and alkyl isonitriles were activated by (tetramesitylporphyrinato)rhodium(II), Rh(tmp), to give rhodium porphyrin silyls or alkyls and rhodium porphyrin cyanide, respectively. Pyridine and triphenylphosphine promoted the rates and yields of the reactions with silylnitriles, but inhibited the rates and yields of the reactions with isonitriles. The reaction of Rh(tmp) with Me3SiCN exhibited second-order kinetics (rate = kobs[Rh(tmp)][Me3SiCN]) at a sufficiently high concentration of pyridine. The reaction with BuNC showed fourth-order kinetics, second-order in each of the reactants; rate = kobs[Rh(tmp)]2[BuNC]2. A novel cyanide transfer rate-determining step was proposed to account for the reaction mechanism.