Racemization of chiral Pd2Au36(SC2H4Ph)24: doping increases the flexibility of the cluster surface

Noelia Barrabés; Bei Zhang; Thomas Bürgi

doi:10.1021/ja507189v

Racemization of chiral Pd2Au36(SC2H4Ph)24: doping increases the flexibility of the cluster surface

J Am Chem Soc. 2014 Oct 15;136(41):14361-4. doi: 10.1021/ja507189v. Epub 2014 Sep 30.

Authors

Noelia Barrabés¹, Bei Zhang, Thomas Bürgi

Affiliation

¹ Department of Physical Chemistry, University of Geneva , 30 Quai Ernest-Ansermet, 1211 Geneva 4, Switzerland.

PMID: 25251045
DOI: 10.1021/ja507189v

Abstract

Pd2Au36(SC2H4Ph)24 clusters have been prepared, isolated and separated in their enantiomers. Compared to the parent Au38(SC2H4Ph)24 cluster, the doping leads to a significant change of the circular dichroism spectrum; however, the anisotropy factors are of similar magnitude in both cases. Isolation of the enantiomers allowed us to study the racemization of the chiral cluster, which reflects the flexibility of the ligand shell composed of staple motifs. The doping leads to a substantial lowering of the racemization temperature. The change in activation parameters due to the doping may be solely due to modification of the electronic structure.