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Alkyne Metathesis Reactions of Rhenium(V) Carbyne Complexes

Authors Bai, Wei HKUST affiliated (currently or previously)
Lee, Ka Ho HKUST affiliated (currently or previously)
Sung, Herman Ho Yung HKUST affiliated (currently or previously)
Williams, Ian D. View this author's profile
Lin, Zhenyang View this author's profile
Jia, Guocheng View this author's profile
Issue Date 2016
Source Organometallics , v. 35, (22), November 2016, p. 3808-3815
Summary Although alkyne metathesis reactions mediated by high-valent d0 carbyne complexes are well established, similar reactions mediated by well-defined low-valent (non-d0) carbyne complexes are rare. This work demonstrates that d2 Re(V) carbyne complexes Re(≡CR)Cl2(PMe2Ph)3 (R = CH2(o-C6H4Br), Ph, CO2Et) can undergo stoichiometric alkyne metathesis reactions. For example, reactions of Re{≡CCH2(o-C6H4Br)}Cl2(PMe2Ph)3 with TMSC≡CR (R = CO2Et, CH2Ph) and PhC≡CPh produced carbyne complexes Re(≡CR)Cl2(PMe2Ph)3 and Re(≡CPh)Cl2(PMe2Ph)3, respectively. Theoretical studies suggest that the metathesis reactions most likely proceed through six-coordinate alkyne-carbyne intermediates Re(≡CR)Cl2(η2-alkyne)(PMe2Ph)2 that undergo reversible cycloaddition reactions. © 2016 American Chemical Society.
ISSN 0276-7333
Language English
Format Article
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