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Ruthenium(II/III) bipyridine complexes incorporating thiol-based imine functions: synthesis, spectroscopic and redox properties

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Title Ruthenium(II/III) bipyridine complexes incorporating thiol-based imine functions: synthesis, spectroscopic and redox properties
 
Creator BHATTACHARYYA, DEBADEEP
CHAKRABORTY, SOMA
MUNSHI, PRADIP
LAHIRI, GOUTAM KUMAR
 
Subject ruthenium(ii/iii)-bipyridine complexes
schiff base ligand
spectroscopic and electrochemical properties
 
Description A group of five new ruthenium(II) bipyridine heterochelates of the type [RuII(bpy)2L]+ 1a–1e have been synthesized (bpy=2,2′-bipyridine; L=anionic form of the thiol-based imine ligands, HS–C6H4N=C(H)C6H4(R) (R=OMe, Me, H, Cl, NO2). The complexes 1a−1e are 1:1 conducting and diamagnetic. The complexes 1a−1e exhibit strong MLCT transitions in the visible region and intra-ligand transitions in the UV region. In acetonitrile solvent complexes show a reversible ruthenium(III)–ruthenium(II) couple in the range 0.2–0.4 V and irreversible ruthenium(III)→ruthenium(IV) oxidation in the range 1.15–1.73 V vs. SCE. Two successive bipyridine reductions are observed in the ranges −1.43 to −1.57 and −1.67 to −1.78 V vs. SCE. The complexes are susceptible to undergo stereoretentive oxidations to the trivalent ruthenium(III) congeners. The isolated one-electron paramagnetic ruthenium(III) complex, 1c+ exhibits weak rhombic EPR spectrum at 77 K (g1=2.106, g2=2.093, g3=1.966) in 1:1 chloroform–toluene. The EPR spectrum of 1c+ has been analyzed to furnish values of distortion parameters (Δ=8988 cm−1; V=0.8833 cm−1) and energy of the expected ligand field transitions (ν1=1028 nm and ν2=1186 nm) within the t2 shell. One of the ligand field transitions has been experimentally observed at 1265 nm.
 
Publisher Elsevier
 
Date 2009-04-03T09:04:14Z
2011-11-25T20:34:31Z
2011-12-26T13:08:17Z
2011-12-27T05:56:17Z
2009-04-03T09:04:14Z
2011-11-25T20:34:31Z
2011-12-26T13:08:17Z
2011-12-27T05:56:17Z
1999
 
Type Article
 
Identifier Polyhedron 18(23), 2951-2959
0277-5387
http://dx.doi.org/10.1016/S0277-5387(99)00204-1
http://hdl.handle.net/10054/1116
http://dspace.library.iitb.ac.in/xmlui/handle/10054/1116
 
Language en