Hexacapped Cubic Transition Metal Clusters and Derivatives a Theoretical Approach

8 Hexacapped Cubic Transition Metal Clusters and Derivatives - a Theoretical Approach 

Regis Gautier, Jean-Frangois Halet and Jean- Yves Saillard 

Ni8( U4-PPh)6(CO)8 (1), characterized by Lower and Dahl 20 years ago is a typical representative example of an empty cubic inorganic transition-metal cluster of formula M8(/i4-E)6Lx (M = transition metal, E = main group element or ligand, L = two-electron terminal ligand (CO, PR3, Cl ...) and x 8). 

The bonding in this type of cluster has been studied by several groups. An EH investigation of related solid-state materials has been performed by Burdett and Miller. Karplus et al. used EH and density functional self-consistent field-multiple scattering-Xa (Xa) calculations to examine the electronic structure of molecular cubic clusters containing a Cog(/i4-S)6 core. More recently, Rosch et al. studied the metal-metal bonding in Nig(/i4-PPh)6(CO)8 with the help of DFT calcula-tions. We recently performed EH and Xa calculations on the whole series of Mg(/i4-E)6L compounds to rationalize their structural arrangement. 

We have shown that such a delocalized MO picture could easily be understood by 

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Gautier R, Halet J-F, Saillard J-Y (1999) Hexacapped cubic transition metal clusters and derivatives a theoretical approach. In Braunstein P, Oro L, Raithby PR (eds) Metal clusters in chemistry, vol 3. Wiley, Weinheim, pp 1643-1663... 

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