Theoretical and Experimental Studies of the Electronic Structure of the Mo3(Micro3-0)(Micro3-OR)(Micro-OR)3(OR)6 Type of Triangulo Metal Atom Cluster Compound

摘要

The electronic structure of a Mo3(Mu sub 3-0) (Mu sub 3-OR) (Mu sub 2-OR)3(OR)6 molecule with R = H, and C3v symmetry, which serves as a model for real molecules in which R = H CH2C(CH)3 or CH(CH3)2 has been calculated by the molecular orbital method of Hall and Fenske. The calculations have been performed not only on the entire molecule, but on the Mo3(12+), Mo3O(OH)(9+) and Mo3O(OH)4(6+) fragments and the metal-metal bonding tracked through these successive stages by the 'clusters in molecules' formalism. In the full molecule, the HOMO is an e orbital that carries most of the e-type M-M bonding, while the a1-type is carried by two MO's, one of which is quite stable. The LUMO is also an e type orbital and the HOMO-LUMO gap is small (ca. 1.5 eV). It is predicted that the Mo3O(OR)10 molecules of this type will have readily accessible redox chemistry in which both oxidation and reduction steps might be slowed or irreversible judging by the character of the HOMO and LUMO of the Mo3O(OR)10 molecule. Experimental observations on Mo3O(ONe)10, Ne = CH2C(CH3)3, are in harmony with this. In addition, the absorption spectrum of Mo3O(ONe)10 has been observed and an assignment based on the calculations in proposed.