Abstract
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.
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