823834-99-7Relevant academic research and scientific papers
Mechanistic studies of Si-CN and C-NC bond activation of silylnitriles and alkyl isonitriles by rhodium porphyrin radical: Novel cyanide transfer
Zhang, Lirong,Fung, Chun Wah,Chan, Kin Shing
, p. 5381 - 5389 (2008/10/09)
The Si-CN and C-NC bonds of silylnitriles and alkyl isonitriles were activated by (tetramesitylpor-phyrinato)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 = k obs[Rh(tmp)]2[BuNC]2. A novel cyanide transfer rate-determining step was proposed to account for the reaction mechanism.
Oxidative addition of silyl cyanides to rhodium porphyrin radical: Isocyanide or cyanide transfer mechanism
Chan, Kin Shing,Zhang, Lirong,Fung, Chun Wah
, p. 6097 - 6098 (2008/10/09)
Rhodium porphyrin radical, coordinated with pyridine, activated the carbon - silicon bond of silyl cyanides to yield rhodium porphyrin silyls and cyanide. The reaction with Me3SiCN exhibited second-order kinetics, rate - kabsd[Rh(tmp)][Me3SiCN], at a sufficiently high concentration of pyridine, and the mechanism was interpreted to involve a cyanide or isocyanide group transfer to rhodium radical.
