Synthesis of new nitrosyl complexes [RuCl3(CNPy)(2)(NO)] (1), [RuCl3(AMPy)(2)(NO)] (2), [RuCl3(CPI)(2)(NO)] (3), [RuCl3(NOPI)(2)(NO)] (4), and [RuCl3(HPI)(2)(NO)] (5) [CNPy = 4-cyanopyridine; AMPy = 4-aminopyridine; CPI = 1-(4-cyanophenyl)-imidazole; NOPI = 1-(4-nitrophenyl)-imidazole; HPI = 1-(4-hydroxyphenyl)-imidazole] has been described. The complexes 1-5 have been characterized by satisfactory elemental analyses, spectral (ESI-MS, FT-IR H-1, C-13 NMR, UV-Vis) and electrochemical studies. Linear nitrosyl group and S-0, state in these complexes have been supported by IR, H-1 NMR spectral studies and X-ray single crystal analyses on representaive complex 1. Photorelease of NO and its trapping by myoglobin have been monitored by UV-Vis studies. Structure of the complexes under investigation has also been supported by theoretical studies. The geometrical parameters of 1-5 are comparable to those obtained from single crystal X-ray diffraction studies on 1. (C) 2012 Elsevier Ltd. All rights reserved.