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Ligand effects in cis-Ru(N-N)2L2 species where N-N is a substituted 2,2′-bisoxazoline and L is monodentate
Authors:Michael GB Drew  Pankaj K Pal
Institution:a School of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK
b Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Calcutta 700 032, India
Abstract: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.
Keywords:Ruthenium  Oxazoline  Crystal structures  Ligand constant  π-Acidity
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