DENSITY-FUNCTIONAL DESCRIPTION OF THE BONDING IN THE MU(3)-CHALCOGENIDOHEXANUCLEAR OCTAHEDRAL CLUSTERS [CO-6(MU(3)-X)(8)(PET(3))(6)] (X=S, SE, TE)

Density functional theory (DFT) in the local density approximation has been applied to describe the bonding in the mu(3)-chalcogenido hexanu clear cobalt clusters of formula [Co-6(mu(3)-X)(8)(PR(3))(6)] (X = S, Se. Te). The geometries of the clusters have been optimised and the bo nding interactions in the sulfide derivative have been analysed using a fragment decomposition scheme. Direct metal-metal interactions are n egligible. The electrochemical behaviour reported for the sulfide clus ter has been rationalised.