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Catalytic Activity of trans-Bis(pyridine)gold Complexes
journal contribution
posted on 2020-03-20, 19:15 authored by Ann Christin Reiersølmoen, Dániel Csókás, Sigurd Øien-Ødegaard, Alan Vanderkooy, Arvind Kumar Gupta, Anna-Carin C. Carlsson, Andreas Orthaber, Anne Fiksdahl, Imre Pápai, Máté ErdélyiGold
catalysis has become one of the fastest growing fields in
chemistry, providing new organic transformations and offering excellent
chemoselectivities under mild reaction conditions. Methodological
developments have been driven by wide applicability in the synthesis
of complex structures, whereas the mechanistic understanding of Au(III)-mediated
processes remains scanty and have become the Achilles’ heel
of methodology development. Herein, the systematic investigation of
the reactivity of bis(pyridine)-ligated Au(III) complexes is presented,
based on NMR spectroscopic, X-ray crystallographic, and DFT data.
The electron density of pyridines modulates the catalytic activity
of Au(III) complexes in propargyl ester cyclopropanation of styrene.
To avoid strain induced by a ligand with a nonoptimal nitrogen–nitrogen
distance, bidentate bis(pyridine)–Au(III) complexes convert
into dimers. For the first time, bis(pyridine)Au(I) complexes are
shown to be catalytically active, with their reactivity being modulated
by strain.