Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions,Organometallics

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Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
Organometallics ( IF 2.5 ) Pub Date : 2021-08-30 , DOI: 10.1021/acs.organomet.1c00425
Dmitry S. Belov ₁ , Didac A. Fenoll ₂ , Indranil Chakraborty ₁ , Xavier Solans-Monfort ₂ , Konstantin V. Bukhryakov ₁

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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.

中文翻译：

钒氧代亚烷基配合物的合成及其在闭环烯烃复分解反应中的反应性

Viimido 亚烷基已被用于涉及环烯烃的开环复分解聚合反应。然而，由于对乙烯的不稳定性，这些配合物在与无环末端烯烃的反应中的应用受到限制。实验和理论研究表明，未取代金属环丁烯的 β-氢化物消除是这些系统中的主要分解途径。在此，我们报告的第一催化活性V的合成氧代亚烷基，VO（CHSiMe ₃）（PET ₃）₂氯，其显示出与已知的V催化剂中闭环复分解反应的各种末端烯烃最高报生产率。提出的 DFT 研究表明，β-氢化物消除明显不利于 V oxo 物种。

更新日期：2021-09-13

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