Dinuclear complexes of (2,2'-bipyridine)(2,2':6',2"-terpyridine)-ruthenium (II) bonded trough cyanide to pentaminoruthenium (II/III) groups

A. BEN ALTABEF; S. R. DE GALLO; M. E. FOLQUER; N. E. KATZ

TRANSITION METAL CHEMISTRY

SPRINGER

Año: 1993 vol. 18 p. 319 - 322

0340-4285

New dinuclcar compleres, containing a Ru(trpy)(bpy)´- moiety (bpy =2,2´-bipyridine. trpy = 2,2´:6´.2-terpyridine) boiided through cyanide to R U ( N H ~ ) ~ ~ +g!ro´ +up s have been prepared and characterized by spectroscopic and elecirochemical techniques. The formation of cyanide bridges isevident from the i.r. and 1i.v.-vis. spectra hy appearance of r(C=N) shifts and changes in i.,,, with respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x boiided through cyanide to R U ( N H ~ ) ~ ~ +g!ro´ +up s have been prepared and characterized by spectroscopic and elecirochemical techniques. The formation of cyanide bridges isevident from the i.r. and 1i.v.-vis. spectra hy appearance of r(C=N) shifts and changes in i.,,, with respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x boiided through cyanide to R U ( N H ~ ) ~ ~ +g!ro´ +up s have been prepared and characterized by spectroscopic and elecirochemical techniques. The formation of cyanide bridges isevident from the i.r. and 1i.v.-vis. spectra hy appearance of r(C=N) shifts and changes in i.,,, with respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x boiided through cyanide to R U ( N H ~ ) ~ ~ +g!ro´ +up s have been prepared and characterized by spectroscopic and elecirochemical techniques. The formation of cyanide bridges isevident from the i.r. and 1i.v.-vis. spectra hy appearance of r(C=N) shifts and changes in i.,,, with respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x respct to lhe mononuclear pareni complcx [Ru(trpy)(bpy) (CN)]´. In lhe mixed-valence species R u b C N Ru; (Ru,- Ru bondcd to bpy, Ru, = Ru bonded to NH,), an intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. with A;,:, = 3.6 x intense metal-to-metal charge transfer transition is observrd a1 j ., = 700nm in MeCN. wit