Abstract
Reaction of Ru(bpy)2Cl2·2H2O with 1,2-bis(trifluoroacetyl)hydrazine H2(adc-CF3) under basic conditions yields the dinuclear (m-adc-CF3)Ru(bpy)222+ ion which was isolated and crystd. for structure detn. in the meso diastereoisomer form as the bis(hexafluorophosphate). The Ru ··Ru distance was detd. at 5.029(1) \AA, and the N-N bond length at 1.463(5) \AA reveals a hydrazido(2-) form of the bridge, implying unchanged metal oxidn. states(II). Besides bpy-based redn., the cyclic voltammetric anal. revealed two oxidn. waves with a (3+) intermediate. Spectroelectrochem. demonstrated that this intermediate (m-adc-CF3)Ru(bpy)223+ with a comproportionation const. of Kc = 108.8, and an absorption at 1680 nm (e = 9900 M-1 cm-1) is a mixed-valent species which is evidenced convincingly from the EPR parameters at g1 = 2.239, g2 = 2.065, g3 = 1.891 (gav = 2.101, Dg = g1 - g3 = 0.348). on SciFinder(R)
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