Alkyne Metathesis Reactions of Rhenium(V) Carbyne Complexes
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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 TMSCCR (R = CO2Et, CH2Ph) and PhCCPh 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.
