TY - JOUR
T1 - Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
AU - Belov, Dmitry S.
AU - Fenoll, Didac A.
AU - Chakraborty, Indranil
AU - Solans-Monfort, Xavier
AU - Bukhryakov, Konstantin V.
N1 - 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
PY - 2021/9/13
Y1 - 2021/9/13
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85114619263&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.1c00425
DO - 10.1021/acs.organomet.1c00425
M3 - Article
AN - SCOPUS:85114619263
VL - 40
SP - 2939
EP - 2944
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 17
ER -