Silver assisted aquation of blue [RuCl(tpy)(RaaiR^´)](ClO₄) (1a-1i) leads to the synthesis of solvento species, blue-violet  [Ru(OH₂)(tpy)(RaaiR^´)](ClO₄)(2a-2i), [RaaiR^´ =p-R-C₆H₅-N=N-C₃H₂-NN, abbreviated as N,N^/-chelator, R = Me, Et, Bz, p-R=H Me, Cl] that have been reacted with NaNO₂in warm EtOH resulting in violet nitro complexes of the type, [Ru(NO₂)(tpy)(RaaiR)](ClO₄)(3a-3i). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the nitro compounds with conc. HClO₄ nitrosyl derivatives, [Ru(NO)(tpy)(RaaiR)](ClO₄)₃ are isolated. The diazotization of the primary aromatic amines with a strongly electrophilic mononitrosyl complex in acetonotrile and dichloromethane solution was thoroughly studied.