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
收藏
页码：3808 / 3815
页数：8
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