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

A group of five new ruthenium(II) bipyridine heterochelates of the type [Ru -II(bpy)(2)L](+) 1a-1e have been synthesized (bpy=2,2'-bipyridine; L=anioni c) form of the thiol-based imine ligands, HS-C6H4N=C(H)C6H4(R) (R=OMe, Me, H, Cl, NO2). The complexes la-le are 1:1 conducting and diamagnetic. The co mplexes la-le exhibit strong MLCT transitions in the visible region and int ra-ligand transitions in the UV region. In acetonitrile solvent complexes s how 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 1.1 5-1.73 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 susce ptible to undergo stereoretentive oxidations to the trivalent ruthenium(III ) congeners. The isolated one-electron paramagnetic ruthenium(III) complex, Ic exhibits weak rhombic EPR spectrum at 77 K (g(1)=2.106, g(2)=2.093, g(3 )=1.966) in 1:1 chloroform-toluene, The EPR spectrum of 1c(+) has been anal yzed to furnish values of distortion parameters (Delta=8988 cm(-1); V=0.883 3 cm(-1)) and energy of the expected ligand field transitions (v(1)=1028 nm and v(2)=1186 nm) within the t(2) shell. One of the ligand field transitio ns has been experimentally observed at 1265 nm. (C) 1999 Elsevier Science L td. All rights reserved.