506
Organometallics 2006, 25, 506-512
Preparation, Characterization, Redox Properties, and UV-Vis-NIR Spectra of Binuclear Ruthenium Complexes [{(Phtpy)(PPh3)2Ru}2{CtC-(CHdCH)m-CtC}]n+ (Phtpy ) 4′-phenyl-2,2′:6′,2′′-terpyridine) Li-Bin Gao,† Sheng-Hua Liu,*,‡ Li-Yi Zhang,† Lin-Xi Shi,† and Zhong-Ning Chen*,† State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002, China, and Key Laboratory of Pesticide & Chemical Biology, College of Chemistry, Central China Normal UniVersity, Wuhan 430079, China ReceiVed September 4, 2005
A series of C4-C10 bridged Ru2II,II complexes [{(Phtpy)(PPh3)2Ru}2(CtC-(CHdCH)m-CtC)]2+ (m ) 0, 1, 2, 3) were prepared by reaction of [(Phtpy)(PPh3)2Ru(acetone)]2+ with Me3Si-CtC-(CHd CH)m-CtC-SiMe3 in the presence of potassium fluoride. Oxidation of the Ru2II,II complexes by 1 equiv of ferrocenium hexafluorophosphate gave the stable Ru2II,III mixed-valence complexes [{(Phtpy)(PPh3)2Ru}2(CtC-(CHdCH)m-CtC)]3+ when m ) 0, 1, or 2. These complexes were all characterized by microanalyses, ESI-MS, 1H and 31P NMR, IR, and UV-vis-NIR spectroscopy, cyclic and differential pulse voltammetry, and X-ray crystallography for compound [1](PF6)2. The wave separations ∆E1/2 (E1/2A - E1/2B) due to stepwise oxidation of two RuII into RuIII are 0.610, 0.260, 0.165, and
