Chalcogen-chalcogen bonds in edge-sharing square-planar d8 complexes.: Are they possible?

A theoretical study of the formation of X-X bonds in complexes with the general formula [M-2(mu-X)(2)L-4] (M = group 10 and X = group 16 elements) having d(8) transition-metal atoms is presented. The existence of two energy minima for some complexes, with short and long X-X distances, is shown by density functional theory calculations, and the factors responsible for it are analyzed, including a strong influence of the nature of the metals and ligands on the relative stability of the two isomers. The influence of the bite angle of chelating terminal ligands and the nature of the donor atom on the relative stabilities of the two isomers are also discussed.