Reactions of hydrolysis of bis-bipyridyl ruthenium (2) complexes

Thermodynamics and kinetics of hydrolysis reactions of cis-[Ru2+(Bipy)2XY]n+ compounds, where X=NO+, Cl-, NO2-; Y=H2O, Cl-, NO2-, OH-, are studied. It is stated that with pH increase in [Ru(Bipy)2·NOCl]2+ solution (except characteristic of nitrozo complexes transformation of nitrozo group to nitronitro group) the complex hydrolysis by chloroligand resulting in the following products: [Ru(Bipy)2NOH2O]3+ (pH≤1); [Ru(Bipy)2NOOH]2+ (pH 3-5);[Ru(Bipy)2NO2H2O]+ (pH7-10); [Ru(Bipy)2NO2OH] (pH>12) takes place. Thermodynamic and kinetic characteristics of the processes in [Ru(Bipy)2·NOCl]2+OH-+H2O system are measured. Hydrolysis of [Ru(Bipy)2Cl2] complex is studied, quantitative characteristics of the process are obtained. It is stated that stability and inertness of chloroligands in bis-bipyridyl ruthenium (2) complexes increases in [Ru(Bipy)2NO2Cl]≅[Ru(Bipy)2Cl2] < [Ru(Bipy)2H2OCl]+ < [Ru(Bipy)2NOCl]2+ series