Stability rules for d5/d6 mixed-valent dimers. Effects from the donor/acceptor capability of the metal (ruthenium vs osmium) and from the occupancy of the mediating ligand orbital (LUMO vs HOMO)
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Inorganic Chemistry 29 (23): 4696--4699 (1990)

Electrochem. stability consts. were detd. for the mixed-valent intermediates in the redox series (bpy)2M(bptz)M(bpy)24+/5+/6+ and (bpy)2M(adc-Me2-)M(bpy)22+/3+/4+; M = Ru, Os; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, adc-Me2- = 1,2-diacetylhydrazido(2-), bpy = 2,2'-bipyridine. The trends obsd. allow the rationalization, in a consistent fashion, the stability of the mixed-valence forms toward disproportionation: The equil. const. Kc depends on the p-donor/p-acceptor character of the metals and on the occupancy and electron population at the coordinating centers of the interacting ligand p orbital. Recent literature examples support this more practically oriented concept, which can be used in the design of new stable mixed-valent complexes. on SciFinder(R)
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