Iron‐Complex‐Catalyzed C-C Bond Cleavage of Organonitriles: Catalytic Metathesis Reaction between H-Si and R-CN Bonds to Afford R-H and Si-CN Bonds
- 21 June 2007
- journal article
- research article
- Published by Wiley in Chemistry – An Asian Journal
- Vol. 2 (7) , 882-888
Abstract
The first example of the catalytic CCN bond cleavage of acetonitrile as well as SiCN bond formation have been achieved in the photoreaction of MeCN with Et3SiH promoted by [Cp(CO)2FeMe]. This catalytic system is applicable to other organonitriles. Several iron complexes [(η5‐C5R5)(CO)2FeR′] (R5=H5, H4Me, Me5, H4SiMe3, H4I, H4P(O)(OMe)2; R′=SiMe3, CH2Ph, Me, Cl, I) were examined as catalyst, and [Cp(CO)2FeMe] was found to be the best precursor. A catalytic reaction cycle was proposed, which involves oxidative addition of Et3SiH to [Cp(CO)FeMe], reductive elimination of CH4 from [Cp(CO)FeMe(H)(SiEt3)], coordination of RCN to [Cp(CO)Fe(SiEt3)], silyl migration from Fe to N in the coordinated RCN, and dissociation of Et3SiNC from Fe. The reaction with MeCN of [Cp(CO)Fe(py)(SiEt3)], which was newly prepared and determined by X‐ray analysis, and the reaction of Et3SiH with MeCN in the presence of a catalytic amount of [Cp(CO)Fe(py)(SiEt3)] showed that the 16‐electron species [Cp(CO)Fe(SiEt3)] is the active species in the catalytic cycle (TON up to 251).Keywords
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