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- W2012156944 abstract "Cationic Rh(III) complex [Cp*(PMe3)Rh(SiPh3)(CH2Cl2)]BAr4‘ (1) activates the carbon−carbon bond of aryl and alkyl cyanides (R−CN, where R = Ph, (4-(CF3)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 h for aryl cyanides, t1/2 < 14 h for alkyl cyanides). 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‘." @default.
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- W2012156944 date "2003-07-19" @default.
- W2012156944 modified "2023-10-11" @default.
- W2012156944 title "A Mechanistic Investigation of the Carbon−Carbon Bond Cleavage of Aryl and Alkyl Cyanides Using a Cationic Rh(III) Silyl Complex" @default.
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- W2012156944 doi "https://doi.org/10.1021/ja034468o" @default.
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