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

作者: Debadeep Bhattacharyya , Soma Chakraborty , Pradip Munshi , Goutam Kumar Lahiri

DOI: 10.1016/S0277-5387(99)00204-1

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摘要: Abstract A group of five new ruthenium(II) bipyridine heterochelates the type [Ru II (bpy) 2 L] + 1a – 1e have been synthesized (bpy=2,2′-bipyridine; L=anionic form thiol-based imine ligands, HS–C 6 H 4 NC(H)C (R) (R=OMe, Me, H, Cl, NO ). The complexes − are 1:1 conducting and diamagnetic. exhibit strong MLCT transitions in visible region intra-ligand UV region. In acetonitrile solvent show a reversible ruthenium(III)–ruthenium(II) couple range 0.2–0.4 V irreversible ruthenium(III)→ruthenium(IV) oxidation 1.15–1.73 vs. SCE. Two successive reductions observed ranges −1.43 to −1.57 −1.67 −1.78 susceptible undergo stereoretentive oxidations trivalent ruthenium(III) congeners. isolated one-electron paramagnetic complex, 1c exhibits weak rhombic EPR spectrum at 77 K ( g 1 =2.106, =2.093, 3 =1.966) chloroform–toluene. has analyzed furnish values distortion parameters Δ =8988 cm −1 ; =0.8833 ) energy expected ligand field ν =1028 nm =1186 nm) within t shell. One experimentally 1265 nm.

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