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.