Abstract
A theoretical study of reaction mechanisms for C–CN bond activation of nitriles by a RhIII–silyl complex is reported. Various mechanisms including direct oxidative addition, insertion of the cyanide C≡N triple bond into the RhIII–silyl bond followed by β-carbon elimination, insertion of the cyanide C≡N triple bond into the RhIII–silyl bond followed by α-carbon elimination (deisocyanide), radical mechanisms, and other possible alternatives have been evaluated. Our results provide strong evidence for the sequential mechanism of cyano insertion/α-C elimination (deisocyanide). The cyanide insertion step should be the rate-limiting step, while the deisocyanide step is facile. The intermediate from cyanide insertion, i.e., the Rh(III) η2-iminoacyl complex, has been identified and is in good agreement with the experimentally characterized X-ray crystal structure. The oxidative addition and cyanide insertion/β-C elimination mechanisms are kinetically inhibited due to extremely high activation barriers. Radical me...
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