Photosubstitution reactions of -[Ru(bpy)(MeCN)] with a pyrazole ligand (pzH) were studied under various conditions toward the development of a photochemical synthetic route to polypyridyl ruthenium complexes (bpy = 2,2'-bipyridine). In the absence of a base, light irradiation of an acetonitrile solution of pyrazole and -[Ru(bpy)(MeCN)] gave a mixture of the reactant and -[Ru(bpy)(pzH)(MeCN)]. In the presence of a mild base such as ,-dimethylaminopyridine, a second photosubstitution from -[Ru(bpy)(pzH)(MeCN)] to -[Ru(bpy)(pz)(pzH)] () was greatly enhanced, as confirmed by UV-vis and H nuclear magnetic resonance spectroscopy. The yields of were increased in solvents with moderate coordinating properties, such as acetone. The successive photosubstitution reaction was observed using a stoichiometric amount of pyrazole.
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