An Ab Initio Study of Structures and Energetics of Copper Sulfide Clusters

Abstract

AbstractThe results of ab initio calculations for the sulfur‐bridged copper clusters [Cu2nSn(PR3)m] (n = 1–4, 6; m = 0, 2, 4, 6, 8; RH, CH3) were compared with those of theoretical investigations of the selenium‐containing analogues that have been recently reported. The theoretical work was carried out in order to find a possible explanation for the experimentally observed–different–properties of both cluster types. The structural principles turned out to be independent of the chalcogen, except the necessary shortening of the copper–chalcogen atomic distance that results from the formal substitution of sulfur for selenium. Comparison of the energetics of the sulfur‐ and selenium‐containing compounds showed that it is necessary to discuss the influence of the tertiary phosphine ligands that protect the existing clusters from reaction to give the solids Cu2S and Cu2Se. However the results of the calculations suggest that the different thermodynamic data of the cluster core and the CuP bonds–at least if PH3 or PMe3 are taken into account–cannot be the only cause for the differences in the experimental behaviour. The responsibility rests rather with kinetic effects, such as the steric demand of the actual ligands or the activation energy of decomposition of the ligand shell during the cluster‐forming reaction.