Article,

Molecular and crystal structures of two mononuclear ruthenium(II) complexes with the strongly p accepting ligand 2,2'-azobis(pyridine) (abpy): mer-Ru(abpy)3(PF6)2 and Ru(abpy)2Cl2 (ctc isomer)

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Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences, 50 (1): 15--22 (1995)
DOI: 10.1515/znb-1995-0104

Abstract

Crystal structure analyses of the title complexes were carried out to establish their mol. configurations. Crystallog. data and at. coordinates are given. The tris(chelate) complex dication in (1)(PF6)2 exhibits a mer configuration of pyridine and azo N atoms in an approx. octahedral arrangement at the metal. The dichlororuthenium bis(chelate) compd. 2 has the halide ligands and the coordinated azo N centers in an equatorial cis arrangement whereas two pyridyl groups (one of each abpy ligand) occupy the axial positions. The bond distances from the metal to the N donor centers are systematically smaller for the stronger p accepting azo functions than for the more basic but less p acidic pyridyl groups, a result which differs from that obtained for Mo(0) and Cu(I) complexes of abpy. All Ru-N distances are shorter in the neutral dichloro complex 2. The noncoordinated pyridyl rings of the potentially tetradentate abpy ligands are tilted into approx. s-cis/(NN-trans)/s-trans positions (dihedral angle w $\approx$ 145°) as to minimize steric repulsion, however, they do not coordinate to the metal (dRu-N \textgreater 327 pm). While there are no significant intermol. interactions, the obsd. conformation implies that considerable structural reorganization is necessary for the formation of oligonuclear complexes. on SciFinder(R)

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