期刊
ORGANOMETALLICS
卷 40, 期 17, 页码 2939-2944出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.1c00425
关键词
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资金
- Florida International University
- U.S. Nuclear Regulatory Commission
- MICINN [PID2020-112715GB-I00]
- Generalitat de Catalunya [2017SGR1323]
This study presents the synthesis of a catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)(2)Cl, which shows the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Theoretical studies suggest that the beta-hydride elimination pathway is significantly disfavored for V oxo species, which may have important implications for future applications in this field.
V imido alkylidenes have been applied for the ringopening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the beta-hydride elimination from unsubstituted metallacyclobutene is the primary decomposition pathway in those systems. Herein, we report the synthesis of the first catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)(2)Cl, which exhibits the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Presented DFT studies indicate that beta-hydride elimination is significantly disfavored for V oxo species.
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