Issue 44, 2010

Chiral undecagold clusters: synthesis, characterization and investigation in catalysis

Abstract

Enantiopure undecagold clusters protected by chiral atropisomeric diphosphine ligands (P⁁P) have been synthesized by the stoichiometric reduction of the corresponding (P⁁P)(AuCl)2 complexes with NaBH4. The molecular mono-disperse [Au11(P⁁P)4Cl2]Cl species have been thoroughly characterized using an array of analytical techniques. 31P NMR experiments suggested the presence of a slow intramolecular ligand exchange process. Circular dichroism measurements showed that enantiomeric clusters display mirror-image chiroptical activity. Such undecagold clusters containing two chloride ligands bound to the peripheral Au(I) atoms were expected to display a carbophilic Lewis acidity similar to the well-documented molecular Au(I) complex catalysts. Chloride abstraction, performed to generate active Au+ sites, induced the Au11 cluster evolution to larger gold clusters and nanoparticles, together with Au(I) complexes, which, in fact, perform the catalysis. This result was corroborated by running an asymmetric tandem hydroarylation-carbocyclization reaction, for which the enantiomeric excesses obtained with Au11 clusters are similar to those reported using Au(I) complexes.

Graphical abstract: Chiral undecagold clusters: synthesis, characterization and investigation in catalysis

Supplementary files

Article information

Article type
Paper
Submitted
30 Apr 2010
Accepted
05 Aug 2010
First published
29 Sep 2010

Dalton Trans., 2010,39, 10608-10616

Chiral undecagold clusters: synthesis, characterization and investigation in catalysis

E. S. Andreiadis, M. R. Vitale, N. Mézailles, X. Le Goff, P. Le Floch, P. Y. Toullec and V. Michelet, Dalton Trans., 2010, 39, 10608 DOI: 10.1039/C0DT00399A

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