431882-35-8Relevant academic research and scientific papers
A mechanistic investigation of the carbon-carbon bond cleavage of aryl and alkyl cyanides using a cationic Rh(III) silyl complex
Taw, Felicia L.,Mueller, Alexander H.,Bergman, Robert G.,Brookhart, Maurice
, p. 9808 - 9813 (2007/10/03)
Cationic Rh(III) complex [Cp*(PMe3)Rh(SiPh 3)(CH2Cl2)]BAr4′ (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF 3)C6H4), (4-(OMe)C6H4), Me, iPr, tBu) to produce complexes of the general formula [Cp*(PMe3)Rh(R)(CNSiPh3)]BAr4′. With the exception of the tBuCN case, every reaction proceeds at room temperature (t1/2 1,2 A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an η1-nitrile species is observed, followed by conversion to an η2-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp* (PMe3)Rh(R)(CNSiPh3)]BAr4′.
