Antiferromagnetic exchange constants were calculated by using the Mulliken-Hush treatment for metal-ligand coupling elements (J. Photochem, Photobiol. A: Chem. 1994, 82, 47) and the valence bond model of antiferromagnetic exchange (Inorg. Chem. 1993, 32, 2850), from the spectral data of the solvent-dependent ligand-to-metal charge-transfer bands of [{(NH3)5Ru}2(μ-L)]4+ complexes, where L is a substituted 1,4-dicyanamidobenzene dianion derivative. These calculated values were compared to the corresponding experimental exchange constants that were estimated from the complexes' solvent-dependent room-temperature magnetic moments. The correlation between these values is quite good, and this in turn implies that a relatively unsophisticated level of theory in conjunction with spectroscopy may be all that is necessary to predict trends in molecular properties derived from frontier orbitals.

Inorganic Chemistry
Ottawa-Carleton Chemistry Institute

Naklicki, M.L. (Mark L.), White, C.A. (Christopher A.), Plante, L.L. (Lisa L.), Evans, C.E.B. (Christopher E. B.), & Crutchley, R. (1998). Metal-Ligand Coupling Elements and Antiferromagnetic Superexchange in Ruthenium Dimers. Inorganic Chemistry, 37(8), 1880–1885.