TY - JOUR AU - Barrabes, Noelia AU - Zhang, Bei AU - Burgi, Thomas TI - Racemization of chiral Pd2Au36(SC2H4Ph)24: Doping increases the flexibility of the cluster surface PY - 2014 JF - Journal of the American Chemical Society JA - J. Am. Chem. Soc. SN - 0002-7863 VL - 136 IS - 41 SP - 14361 EP - 14364 L1 - http://pubs.acs.org/doi/pdf/10.1021/ja507189v L2 - http://pubs.acs.org/doi/full/10.1021/ja507189v L3 - http://pubs.acs.org/doi/abs/10.1021/ja507189v L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01437.png M3 - 10.1021/ja507189v UR - http://dx.doi.org/10.1021/ja507189v N2 - 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 dichrosim spectrum, however, the anisotropy factors are of similar magnitude in both cases. Isolation of the enantiomers allowed us to study the racemi-zation 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. ID - 1437 ER -