Bonding Analysis in Inorganic Transition-Metal Cubic Clusters, 5 M8((mu)8-E)((mu)4-E)6L8 Species Centered and Hexacapped by Main-Group Atoms

The mono- and bidentate chelation of the main-group elements silicon, germanium, tin, and lead through the phosphorus atoms of the diphosphanylmethanide ligand has been studied by means of quantum chemical methods. In accord with experimental investigations, the species are found to adopt a (psi)-tbp conformation of high flexibility. The various distortional modes causing the axial and equatorial positions to become equivalent have also been investigated. In addition, the bonding situations in the electronically related bis(diamino)- and the higher element homologue bis(diarsanyl)methanide ligand systems have been studied. The bonding situation in the hitherto experimentally unknown bis(diamino)methanide ligands is predicted to be similar to that in bis(amidinate) complexes. An analysis of the electron distributions (natural bond orbital population analysis) in these compounds reveals that the central main-group element is positively charged and weakly chelated by the surrounding ligands.