Ligand effects in cis-RuII(N–N)2L2 species where N–N is a substituted 2,2′-bisoxazoline and L is monodentate

Starting from previously reported cis-Ru(MeL)2Cl2, where MeL is 4,4,4′,4′-tetramethyl-2,2′-bisoxazoline, cis-Ru(MeL)2Br2 (1), cis-Ru(MeL)2I2 (2), cis-Ru(MeL)2(NCS)2 · H2O (3), cis-Ru(MeL)2(N3)2 (4) and cis-[Ru(MeL)2(MeCN)2](PF6)2 · (CH3)2CO (5) are synthesised. The X-ray crystal structures of complexes 1, 2, 3 and 5 have been determined. All the five new complexes have been characterized by FTIR, ESIMS and 1H NMR. In cyclic voltammetry in acetonitrile at a glassy carbon electrode, the complexes display a quasireversible Ru(II/III) couple in the range 0.32–1.71 V versus NHE. The Ru(II/III) potentials yield a satisfactorily linear correlation with Chatt’s ligand constants PL for the monodantate ligands. From the intercept and by comparing the known situation in Ru(2,2′-bipyridine)2L2, it is concluded that MeL, a non-aromatic diimine, is significantly more π-acidic than 2,2′-bipyridine.