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.
INDIANA UNIV AT BLOOMINGTON DEPT OF CHEMISTRY
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The electronic structure of a Mo3Mu sub 3-0 Mu sub 3-OR Mu sub 2-OR3OR6 molecule with R H, and C3v symmetry, which serves as a model for real molecules in which R H CH2CCH3 or CHCH32 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 Mo312, Mo3OOH9 and Mo3OOH46 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 MOs, 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 Mo3OOR10 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 Mo3OOR10 molecule. Experimental observations on Mo3OONe10, Ne CH2CCH33, are in harmony with this. In addition, the absorption spectrum of Mo3OONe10 has been observed and an assignment based on the calculations in proposed.
- Physical Chemistry