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Synthesis, characterization and redox properties of ruthenium(II) dithiocarbonato complexes having 2,2'-bipyridine coligands

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Title Synthesis, characterization and redox properties of ruthenium(II) dithiocarbonato complexes having 2,2'-bipyridine coligands
 
Creator THAKUR, GA
NARAYANASWAMY, K
LAHIRI, GK
 
Subject polypyridine complexes
charge-transfer
electrochemistry
parameters
chemistry
resonance
oxidation
spectra
ru(ii)
osmium
 
Description A group of stable new ruthenium (II) mixed tris-chelated complexes of the type [Ru(bpy)(2)(L)]ClO4 . 2H(2)O, [bpy:2,2'-bipyridine; L:anionic form of KSSCOR, R = Me, Et, (n)pr, (n)Bu] have been prepared by the reaction of Ru(bpy)(2)CO3 with KSSCOR in methanol. The complexes are essentially diamagnetic and behave as 1:1 electrolytes in CH3CN. All the complexes show metal to ligand charge transfer transitions in the visible region (495-450 nm). The complexes do not exhibit any emission spectra at room temperature. The geometry of the complexes has been assessed by high-resolution H-1 NMR spectroscopy. Reductions of coordinated bpy units are observed in the range -1.5 and -1.8 V, respectively. All the complexes exhibit one reversible ruthenium (II)-ruthenium(III) oxidation couple near 0.7 V (versus SCE) in acetonitrile solution at platinum electrode. Coulometric oxidation of [Ru-II(bpy)(2)(L)](+) at 0.9 V.(vs. SCE) as well as chemical oxidation by Ce(IV) in 0.1M aqueous HClO4 produces unstable green coloured ruthenium(III) congener of [Ru-II(bpy)(2)(L)(+) i.e. [Ru-III(bpy)(2)(L)](+2). The presence of trivalent ruthenium in the oxidized solution is evidenced by the rhombic EPR spectrum with g values (g(1) = 2.720, g(2) = 2.370 and g(3) = 1.700).
 
Publisher COUNCIL SCIENTIFIC INDUSTRIAL RESEARCH
 
Date 2011-07-21T03:13:30Z
2011-12-26T12:51:51Z
2011-12-27T05:38:31Z
2011-07-21T03:13:30Z
2011-12-26T12:51:51Z
2011-12-27T05:38:31Z
1996
 
Type Article
 
Identifier INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY, 35(5), 379-384
0376-4710
http://dspace.library.iitb.ac.in/xmlui/handle/10054/5759
http://hdl.handle.net/10054/5759
 
Language en