Issue 16, 1999

Structure, spectroscopic and electrochemical properties of novel binuclear ruthenium(II) copper(I) complexes with polypyridyl bridging ligands

Abstract

Binuclear complexes of the type [(bpy)2Ru(BL)Cu(PPh3)2]3+, where bpy = 2,2′-bipyridine, BL = 2,3-di-2-pyridylpyrazine (dpp), 2,3-di-2-pyridylquinoxaline (dpq), or 6,7-dimethyl-2,3-di-2-pyridylquinoxaline (dpqMe2), were readily formed by the reaction of [Cu(PPh3)4]+ with mononuclear complexes [Ru(bpy)2(BL)]2+. The binuclear complexes are stable in CH2Cl2 solution at concentrations above 10–3 mol dm–3 having equilibrium constants for formation in the range 1000–2500 dm3 mol–1. Single crystal structures for [(bpy)2Ru(dpp)Cu(PPh3)2]3+ and [(bpy)2Ru(dpqMe2)Cu(PPh3)2]3+ show distortions of the bridging ligand in the form of twisting and splaying of the ring systems. Electrochemical and UV/Visible data suggest the {Cu(PPh3)2}+ moiety has little affect in stabilising the BL π* orbital. Resonance Raman spectra show the bichromophoric nature of the visible absorptions of the heteroleptic complexes; both bpy and BL ligand vibrations are enhanced depending on the excitation wavelength. Observation of a Ru–N vibration suggests that the dominant transition in the visible region is Ru(dπ)→BL(π*) CT.

Supplementary files

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1999, 2669-2673

Structure, spectroscopic and electrochemical properties of novel binuclear ruthenium(II) copper(I) complexes with polypyridyl bridging ligands

S. M. Scott, K. C. Gordon and A. K. Burrell, J. Chem. Soc., Dalton Trans., 1999, 2669 DOI: 10.1039/A902934F

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