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Iron-Complex-Catalyzed CC Bond Cleavage of Organonitriles: Catalytic Metathesis Reaction between HSi and RCN Bonds to Afford RH and SiCN Bonds
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...
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Published in: | Chemistry, an Asian journal an Asian journal, 2007-07, Vol.2 (7), p.882-888 |
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Main Authors: | , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | 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).
Bond exchange: Catalytic CC bond cleavage of acetonitrile and CSi bond formation can be attained by the photoreaction of MeCN with Et3SiH in the presence of [Cp(CO)2FeMe]. This catalytic system is also applicable to other organonitriles. |
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ISSN: | 1861-4728 1861-471X |
DOI: | 10.1002/asia.200700076 |