Summary
New dinuclear complexes, containing a Ru(trpy)(bpy)2+ moiety (bpy = 2,2′-bipyridine, trpy = 2,2′:6′,2′'-terpyridine) bonded through cyanide to Ru(NH3) sup2+/3+inf5 groups have been prepared and characterized by spectroscopic and electrochemical techniques. The formation of cyanide bridges is evident from the i.r. and u.v.-vis. spectra by appearance of v(C≡N) shifts and changes in λmax with respect to the mononuclear parent complex [Ru(trpy)(bpy) (CN)]+. In the mixed-valence species Ru supIIinfb —CN—Ru supIIIinfa (Rub = Ru bonded to bpy, Rua = Ru bonded to NH3), an intense metal-to-metal charge transfer transition is observed at λmax = 700 nm in MeCN, with Δovv 1/2 = 3.6 × 103 cm−1. From these spectral data and the difference in redox potentials between both metallic centres (determined by c.v. to be ΔE 1/2 = 1.19 V), a value of k th,r = 5 × 105 s-1 has been calculated for the rate of thermal intramolecular electron transfer of the reverse process: Ru supIIina → Ru supIIIinb . This low value suggests an ‘inverted regime’. The complexes studied are thus interesting as models for the design of energy conversion schemes.
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Presented in part at the XIX Latinoamerican Congress on Chemistry, Buenos Aires, Argentina, November 1990.
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Ben Altabef, A., Ribotta de Gallo, S.B., Folquer, M.E. et al. Dinuclear complexes of (2,2′-bipyridine)(2,2′:6′,2′'-terpyridine)-ruthenium(II) bonded through cyanide to pentaammineruthenium(II/III) groups. Transition Met Chem 18, 319–322 (1993). https://doi.org/10.1007/BF00207956
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DOI: https://doi.org/10.1007/BF00207956