Heteroleptic Complexes of Ruthenium Nitrosyl with Pyridine and Bypiridine-Synthesis and Photoisomerization.

ABSTRACT

The reaction of [RuNO(Py)2Cl2OH] with bipyridine in water-ethanol media results in trans-(NO, OH)-[RuNO(Py)(Bpy)ClOH]+ with an acceptable yield (60-70%) as hexafluorophosphate salt. Further treatment of the hydroxy-complex with concentrated HF quantitatively leads to trans-(NO, F)-[RuNO(Py)(Bpy)ClF]+. Despite the chirality of both coordination spheres, the hexafluorophosphate salts crystallized as racemates. A NO-linkage isomerism study of the obtained complexes was performed at 80 K with different excitation wavelengths (405, 450, 488 nm). The most favorable wavelengths for the MS1 isomer (Ru-ON) formation were 405 and 450 nm, where the linkage isomer populations were 17% and 1% for [RuNO(Py)(Bpy)ClOH]PF6 and [RuNO(Py)(Bpy)ClF]PF6. The shift of the excitation wavelength to the green (488 nm) sharply decreased the MS1 population. The IR-spectral signatures of MS1 were registered. Reverse-transformation Ru-ON (MS1)-Ru-NO (GS) was investigated for [RuNO(Py)(Bpy)ClOH]PF6 using IR and DSC techniques that made it possible to determine the kinetic parameters (Ea and k0) and decay temperature.