Article,

Characterization of the mixed-valent intermediate (n = 3) of the complex series (μ,η3:η3-L)Ru(terpy)2n+ with the unsaturated bridging ligand N,N'-bis(a-picolinoyl)hydrazido(2-) = L2-

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Polyhedron, 23 (4): 701--707 (2004)
DOI: 10.1016/j.poly.2003.11.043

Abstract

N,N'-Bis(a-picolinoyl)hydrazine (H2L), a potentially bis-tridentate conjugated ligand in its doubly deprotonated form L2-, was used to synthesize the diruthenium(II) complex (μ-L)Ru(terpy)2(PF6)2. Its electrochem. and spectroelectrochem. (UV-visible-NIR, EPR) study reveals a mixed-valent (RuIIIRuII) intermediate with electrochem. and spectroscopic characteristics related to those of the (μ-adc-R)Ru(bpy)223+ ions (adc-R2-= bis-bidentate C-substituted diacylhydrazido(2-) ligands): comproportionation const. Kc = 109.0 (CH2Cl2), intervalence charge transfer band at 1000 nm (e=3800 M-1 cm-1), EPR signal at g$\bot$ = 2.14, g‖ = 1.953. The noninnocent nature of Ln- is inferred from comparative anal. of the spectroscopic data. on SciFinder(R)

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