Ruthenium(II) nitro-nitroso-bis-{1-(alkyl)-2-(β-napthylazo)imidazole}: Synthesis, spectroscopy, electrochemistry and reactivity

Abstract

Aquation of blue cis-trans-cis-[RuCl2(β-NaiR)2] (1) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH2)2(β-NaiR)2](ClO4)2 (2), [β-NaiR = C10H7-N=N-C3H2-NN, abbreviated as N,N′-chelator, R = Me] that have been reacted with NaNO2 in warm EtOH resulting in violet dinitro complexes of the type, [Ru(NO2)2(β-NaiR)2] (3). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the dinitro compounds with cone. HClO4 nitro-nitrosyl derivatives, [Ru(NO2)(NO)(β-NaiR)2]2+ (4) are isolated. The chemical oxidation of aqua complex (2) by excess aqueous eerie solution in 1 (N) H2SO4 leads to the spontaneous formation of a yellow colored species. The electrophilic behaviour of metal bound nitrosyl has been proved by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group. The diazotization of the primary aromatic amines with a strongly electrophilic mononitrosyl complex in acetonotrile and dichloromethane solution was thoroughly studied. Electrocatalytic oxidation of benzyl alcohol was examined.