Alkyne Metathesis Reactions of Rhenium(V) Carbyne Complexes

被引：15

作者：

Bai, Wei ^{[1
]}

Lee, Ka-Ho ^{[1
]}

Sung, Herman H. Y. ^{[1
]}

Williams, Ian D. ^{[1
]}

Lin, Zhenyang ^{[1
]}

Jia, Guochen ^{[1
]}

机构：

[1] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

来源：

ORGANOMETALLICS | 2016年 / 35卷 / 22期

关键词：

METAL-CARBON BONDS; MAIN-GROUP ELEMENTS; TRIALKOXYMOLYBDENUM(VI) ALKYLIDYNE COMPLEXES; OLEFIN METATHESIS; HYDRIDO ALKENYLCARBYNE; ETA(2)-VINYL COMPLEXES; BENZYLIDYNE COMPLEXES; CARBENE COMPLEXES; CRYSTAL-STRUCTURE; CROSS-METATHESIS;

D O I：

10.1021/acs.organomet.6b00653

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Although alkyne metathesis reactions mediated by high-valent d(0) carbyne complexes are well established, similar reactions mediated by well-defined low-valent (non-d(0)) carbyne complexes are rare. This work demonstrates that d(2) Re(V) carbyne complexes Re( CR)Cl-2(PMe2Ph)(3) (R = CH2(o-C6H4Br), Ph, CO2Et) can undergo stoichiometric alkyne metathesis reactions. For example, reactions of Re{ CCH2(o-C6H4Br)}Cl-2(PMe2Ph)(3) with TMSC CR (R = CO2Et, CH2Ph) and PhC CPh produced carbyne complexes Re( CR)Cl-2(PMe2Ph)(3) and Re( CPh)Cl-2(PMe2Ph)(3), respectively. Theoretical studies suggest that the metathesis reactions most likely proceed through six-coordinate alkyne-carbyne intermediates Re( CR)Cl-2(eta(2)-alkyne)(PMe2Ph)(2) that undergo reversible cydoaddition reactions.

引用

页码：3808 / 3815

页数：8

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