Ab initio SCF and DFT models of met-car adducts: Ti 8C 12(L) n (L = Cl, NH 3, CO, C 6H 6; n = 4, 8)

Abstract

The addition of Cl, NH 3, CO, C 6H 6 to Ti 8C 12 has been investigated by means of ab initio RHF and DFT calculations. The metallocarbohedrene (met-car) molecule has been modelled as a structure of a tetracapped tetrahedron with T d symmetry and two distinct metal sites, found to be most stable from previous theoretical investigations. The addition of four molecules to the atoms of the external tetrahedron of metal atoms has been found to be exothermic for all ligands considered. The addition of four extra ligands leading to T 8C 12(L) 8 appears easy for L  Cl, and also for L  NH 3. It appears that π-bonding molecules, either non-polar like benzene or weakly polar like CO, have much less affinity for the inner tetrahedron of metal atoms, which makes adducts with eight ligands difficult or impossible to obtain in that case. Those results agree with the recently observed reactivity of met-cars.