The reaction of ctc-[Ru(R-aapm)₂Cl2] (1) with (NH₄)₂MoS₂ in aqueous MeOH afforded redviolet mixed ligand complexes of the type [(R-aapm)₂Ru(μ-S)₂Mo(OH)₂] (2a-2e) [R-aapm = 2-(arylazo) pyrimidine,p-R-C₆H₄-N=N-C₄H₃NN, R = H (2a), Me (2b), Cl (2c), OMe (2d), NO₂ (2e)]. In complexes (2a-2e) the terminal Mo=S bonds of the MoS unit get hydroxylated and the molybdenum ion is reduced from the starting Mo^VI in MoS to Mo^IV in the final product. The solution electronic spectra ex-hibit a strong MLCT band at 550–570 nm in DCM. The¹H NMR spectra confirms the geometry of the complexes as being that ofcistranscis isomers. Cyclic voltammograms show a Ru(III)/Ru(II) couple at 1.10–1-4 V, irreversible Mo(IV)/Mo(V) oxidations in the 1.66–1.72 V range, along with four successive reversible ligand reductions in the range -0.45–0.67 V (one electron), -0.82–1.12 V (one electron),-1.44–1.90 V (simultaneously two electrons).

Reaction of [Au^III(C₆F₅)₃(tht)] with RaaiR′ in dichloromethane medium leads to [Au^III(C₆F₅)₃ (RaaiR′)] [RaaiR′=p-R-C₆H₄-N=N-C₃H₂-NN-l-R′, (1-3), R = H (a), Me (b), Cl (c) and R′= Me (1), CH₂CH₃ (2), CH₂Ph (3), tht is tetrahydrothiophen]. The nine new complexes are characterised by ES/MS as well as FAB, IR and multinuclear NMR (¹H,¹³C,¹⁹F) spectroscopic studies. In addition to dimensional NMR studies as¹H,¹H COSY and¹H¹³C HMQC permit complete assignment of the complexes in the solution phase.

Silver-assisted aquation of bluecis-trans-cis-RuCl₂(Raapm)₂ (1a-1e) leads to the synthesis of solvento species, blue-violetcis-trans-cis-[Ru(OH₂)₂(Raapm)₂](ClO₄)₂ [Raapm =p-R-C₆H₄-N=N-C₄H₃-NN, (2a-2e), abbreviated as N,N′-chelator, where N(pyrimidine) and N(azo) represent N and N′ respectively; R = H (a),p-Me (b),p-Cl (c),m-Me (d),m-Cl (e) that react with NO₂ in warm EtOH to give violet dinitro complexes of the type, Ru(NO₂)₂(Raapm)₂ (3a-3e). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the dinitro compounds with conc. HClO₄, nitro-nitrosyl derivatives are isolated. The solution structure and stereoretentive transformation in each step have been established from¹H NMR results. The compounds are redox active and display one metal-centred oxidation and successive ligand-based reductions. The v (NO) > 1900 cm^-1 strongly suggests the presence of linear Ru-N-O bonding. The electrophilic behaviour of metal-bound nitrosyl has been proved in one case by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group. Diazotization of primary aromatic amines with strongly electrophilic mononitrosyl complexes in acetonotrile and dichloromethane solutions has been thoroughly studied.