Dissociation of Bipyridine and Coordination with Nitrosyl: Cyclometalated Ruthenium Nitrosyl Complex

A novel family of ruthenium nitrosyl complexes [Ru(bpy)(C^∧N)(MeCN)NO](PF₆)₂ (2a-2e, bpy = 2,2'-bipyridine, HC^∧N = 2-phenylpyridine and its derivatives) has been prepared by reacting cyclometalated ruthenium complexes [Ru(bpy)₂(C^∧N)][PF₆] (1a-1e) with NO⁺, which were comprehensively characterized by mass, IR, NMR, and UV-vis spectra as well as the single-crystal X-ray structure determinations. Herein, the coordination geometry of Ru atoms in 2a-2e is a distorted octahedron and {Ru^II-NO⁺}⁶ is present in these complexes. Theoretical calculations suggest that the reactions involving dissociation of one bipyridine and coordination with NO⁺ proceed spontaneously (ΔG < 0) and the transformation from 1a-1e to the intermediates is dominated by substituents (ΔG_RI varies from -1.19 to -1.53 eV), which influence the binding energy between Ru(II) and NO⁺ in complexes 2a-2e (-89.42 to -101.17 kcal/mol) and thus control the photorelease of NO on a certain scale. The weak absorption bands in the visible region could be attributed to the contribution of dπ(Ru^II) → π*(NO⁺), which were enhanced greatly under light, indicating the possible release of NO. The photoinduced NO, as well as singlet oxygen (¹O₂), was then confirmed by EPR spectra, and the amount of NO released from 2a-2e was estimated via Griess reagent assay. The cytotoxicity of these complexes with or without visible light irradiation was also investigated using an MTT assay.