Cyclometalated ruthenium chloro and nitrosyl complexes

The novel cyclometalated Ru(III) complex, [Ru(eta(2)-phpy)(trpy)Cl][PF6].toluene 1, and the {Ru-NO}(6) complex, [Ru-(eta(2)-phpy)(trpy)NO][PF6](2) 2, where trpy is 2,2': 6',2-terpyridine and phpy is 2-phenylpyridine, have been prepared and characterized by elemental analysis, IR, H-1 NMR, and electronic absorption spectroscopies, cyclic voltammetry, and crystallography. The crystal structure of 1 showed the chloride ion trans to the sigma-bonding phenyl group of phpy and is an unusual example of a stable paramagnetic cyclometalated complex. The crystal structure of 2 shows the nitrosyl ligand trans to the sigma-bonding phenyl group of phpy. The significant distortion of the normally linear Ru-NO bond angle (167.1 (4)degrees) can be largely ascribed to the strong sigma-donor properties of the phenyl group.