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Updated: Mar 11, 2026

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Phosphinines versus mesoionic carbenes: a comparison of structurally related ligands in Au(i)-catalysis
Massimo Rigo1, Lara Hettmanczyk1, Frank J L Heutz2
1Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany. Biprajit.Sarkar@fu-berlin.de c.mueller@fu-berlin.de.
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.
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