Abstract
An analysis of the electronic structures of members of the series of complexes [Ru(bipy) 3− n (ppy) n ] (2− n)+ (bipy = 2,2′-bipyridine and Hppy = 2-phenylpyridine) is presented. The cyclometallated complexes (i.e. those in which one or more [ppy] − replace bipy ligands) exhibit a distinct separation of RuC and RuN σ-bonding character, and in cis-[Ru(bipy)(ppy) 2], further separation of bonding character occurs to give MO's which possess either RuC, RuN [ppy] − , or RuN bipy components. Comparisons of the cis- and trans-isomers of [Ru(bipy)(ppy) 2] and of the fac- and mer-isomers of [Ru(ppy) 3] − suggest that the observed experimental preference for cis- over trans- and fac- over mer-structures may be due to the enhanced σ-donating ability of the carbon atom when it resides trans to a nitrogen rather than carbon donor.
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