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)

, , und . Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences 50 (1): 15--22 (1995)


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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