Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
Belov, Dmitry S. (Florida International University. Department of Chemistry and Biochemistry)
Fenoll, Didac A. (Universitat Autònoma de Barcelona. Departament de Química)
Chakraborty, Indranil (Florida International University. Department of Chemistry and Biochemistry)
Solans Monfort, Xavier (Universitat Autònoma de Barcelona. Departament de Química)
Bukhryakov, Konstantin V. (Florida International University. Department of Chemistry and Biochemistry)

Date:	2021
Abstract:	V imido alkylidenes have been applied for the ring-opening 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 β-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)2Cl, which exhibits the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Presented DFT studies indicate that β-hydride elimination is significantly disfavored for V oxo species.
Grants:	Agencia Estatal de Investigación PID2020-112715GB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1323
Note:	Funding Information: We are grateful to the Florida International University and the New Faculty Development Grant provided by U.S. Nuclear Regulatory Commission for financial support. Financial support from MICINN [PID2020-112715GB-I00] and the Generalitat de Catalunya [2017SGR1323] are also gratefully acknowledged. Publisher Copyright: © 2021 American Chemical Society
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Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Published in:	Organometallics, Vol. 40, Issue 17 (September 2021) , p. 2939-2944, ISSN 1520-6041

DOI: 10.1021/acs.organomet.1c00425

Postprint 7 p, 1.7 MB

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