Phosphinines versus mesoionic carbenes: a comparison of structurally related ligands in Au(i)-catalysis

Abstract

Gold(I) complexes based on a 2,4,6-triarylphosphinine and a mesoionic carbene derivative have been prepared and characterized crystallographically. Although structurally related, both heterocycles differ significantly in their donor/acceptor properties. These opposed electronic characteristics have been exploited in Au(I)-catalyzed cycloisomerization reactions. For the conversion of the standard substrate dimethyl 2-(3-methylbut-2-enyl)-2-(prop-2-ynyl)malonate the results obtained for both Au-catalysts were found to be very similar and comparable to the ones reported in the literature for other carbene- or phosphorus(III)-based Au(I)-complexes. In contrast, a clear difference between the catalytic systems was found for the cycloisomerization of the more challenging substrate N-2-propyn-1-ylbenzamide. A combination of the phosphinine-based complex and [AgSbF₆] or [Cu(OTf)₂] leads to a catalytic species, which is more active than the mesoionic carbene-based coordination compound. We attribute these differences to the stronger π-accepting ability of phosphinines in comparison to mesoionic carbenes. The here presented results show for the first time that phosphinines can be used efficiently as π-accepting ligands in Au(I)-catalyzed cycloisomerization reactions.