431882-29-0

Upstream product

• 630-18-2 tert-butyl isocyanide 
• 431882-00-7 [(C₅(CH₃)5)(P(CH₃)3)Rh(CH₃)(dichloromethane)][B(3,5-C₆H₃(CF₃)2)4] 
• 789-25-3 HSiPh₃ 
• 431882-02-9 [(C₅(CH₃)5)(P(CH₃)3)Rh(Si(C₆H₅)3)(dichloromethane)][B(3,5-C₆H₃(CF₃)2)4] 
• 431882-26-7 [(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(η1-NCC(CH3)3)][B(3,5-C6H3(CF3)2)4] 

Relevant 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

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′.

Carbon-carbon bond activation of R-CN (R = ME, Ar, iPr, tBu) using a cationic Rh(III) complex

Addition of 1.0 equiv of Ph3SiH to [Cp*(PMe3)Rh(Me)(CH2Cl2)]+BAr'4- (1) resulted in release of methane and quantitative formation of [Cp*(PMe3)Rh(SiPh3)(CH2