Electronic Spectroscopy and the Photochemistry of Compounds which Contain Quadruple Metal-Metal Bonds

Author: Trogler, William Charles

Year: 1978

Degree: Dissertation (Ph.D.)

Advisor: Gray, Harry B.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/nr7a-jz27

Abstract

The electronic spectra and structures of binuclear transition metal compounds which contain a quadruple metal-metal bond are discussed. Experimental results are presented for the electric-dipole forbidden transitions of (n-Bu4)2[Re2Cl8], (n-Bu4)2[Re2Br8], Mo2(O2CCH3)4, Mo2(O2CCD3)4, Mo2(O2CH)4, and Mo2(O2CCF3)4. The near infrared absorption system in K3Mo2(SO4)4 · 3.5 H2O has also been analyzed.

Aqueous acid solutions of Mo2(SO4)44-, Mo2(aq)4+, and Mo2Cl84- yield molecular hydrogen and oxidized molybdenum products upon ultraviolet irradiation. The compounds Mo2Cl4P4 (P = P(n-Bu)3, P(Et)3 and P(Et)(Ph)2) undergo photooxidation to chloride bridged binuclear Mo(III) compounds subsequent to 254 nm irradiation in chlorocarbon solvents. The nature of these photooxidation reactions are examined.

Files