Abstract

Rhenium(V) carbyne complexes are potential alkyne metathesis catalysts with the advantage of robustness to water and wide range of substrates. One of the limitations of these catalyst candidates is the time-consuming and tedious preparation of their rhenium carbyne precursor. We have recently found that one-pot reactions of the rhenium(III) phosphine starting materials 1 with phosphine and TMSC≡CH can give cationic rhenium(V) carbyne complexes 2 with decent yields. The reaction involves 1,2-H (or TMS) shift of a transient rhenium η²-vinyl intermediate, generated by the nucleophilic phosphine attack on a coordinated alkyne. The isolated cationic rhenium carbyne complexes 2 were tested for ligand modification and alkyne metathesis reactions. The results of the investigation will be reported in this presentation.