Cyclometalated ruthenium chloro and nitrosyl complexes

The novel cyclometalated RU(III) complex, [Ru(η2-phpy)(trpy)Cl][PF6]·toluene 1, and the {Ru-NO}6 complex, [Ru-(η2-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, 1H NMR, and electronic absorption spectroscopies, cyclic voltammetry, and crystallography. The crystal structure of 1 showed the chloride ion trans to the σ-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 σ-bonding phenyl group of phpy. The significant distortion of the normally linear Ru-NO bond angle (167.1(4)°) can be largely ascribed to the strong σ-donor properties of the phenyl group