Cyclometalated ruthenium chloro and nitrosyl complexes

The novel cyclometalated Ru(III) complex, Ru(eta(2)-phpy)(trpy)Cl]PF(6)].toluene 1, and the Ru-NO](6) complex, Ru(eta(2)-phpy)(trpy)NO]PF(6)](2) 2, where trpy is 2,2': 6',2'-terpyridine and phpy is 2-phenylpyridine, have been prepared and characterized by elemental analysis, IR, (1)H 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.