Stepwise alkyne insertion in Au(i) acetylides: influence of the nuclearity.

ABSTRACT: The reaction between NHC-supported (NHC = N-heterocyclic carbene) gold(i) trimethylsilylacetylide complexes with NHC gold(i) hydroxide species renders different symmetrical homobimetallic Au complexes. These compounds readily undergo migratory insertion of DMAD (dimethyl acetylenedicarboxylate) at 25 °C to give the corresponding bimetallic enyne products. On the contrary, monometallic analogues require much more forcing conditions (excess of DMAD and temperature ≥110 °C) to give the same transformation. Experimental and computational studies reveal that the second metal fragment is responsible for the enhanced nucleophilicity of the reactive carbon atom of the acetylide C[triple bond, length as m-dash]C bond, which initially leads to a more favorable interaction with DMAD in the rat

SUBMITTER: Cayuela-Castillo J 

PROVIDER: S-EPMC11824391 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature