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The reaction of 2-(arylazo) aniline with RhCl(sub3) afforded new cyclometalated complexes of Rh(III), (L)(HL)Rh(super III)Cl(sub2) and (L)(ArNH(sub2)Rh(super III)Cl(sub2).The formation of (L)(HL)Rh(super III)Cl(sub2) and (L)(ArNH(sub2)Rh(super III)Cl(sub2) indicated azo (-N=N-) bond cleavage of 2-(arylazo) aniline.

The azo-amine system in the form of electroneutral diamagnetic bis chelates of palladium is presented. The chelated azo amines incorporate 10 ligand pi electrons while their synthetic precursor is the bis(azooximate) Pd-(Ra)2. The azo-amine frame can be looked upon as the intermediate member in the azo-azo, azo-amine, imine-imine sequence. Results with palladium indicate that the chelate frame can sustain more ligand pi electrons and anionic charge as the number of nitrogen increases.

Spectroscopic studies of ruthenium complexes of the type RuN4P2 containing the Ru(PPh3)2 moiety reveal the presence of an intense near-IR LMCT band. The voltammograms of Ru(II) and Ru(III) are identical due to their invariant geometry. Crowding by PPh3 and other such functions leads to destabilization of the bi- and trivalent cis geometries. The trans geometry of the bivalent state possess back-bonding, while that of the trivalent state does not.

A one-electron-one-proton electroprotic transformation enables the conversion of trans-Pt(pbo)2 (Hpbo = PhN double bond Nc(Ph) double bond NOH), prepared from a reaction between Hpbo and K2PtCl4, into a cis-dimer complex. Both trans and cis complexes exhibit diamagnetism in the solid state, and in solution the dimer undergoes dissociation. X-ray and spectroscopic studies help characterize these complexes. In the dimer, dz2-dz2 and azo-azo interactions exhibit significant contribution to binding, while the unpaired electron in the monomer is significantly azo-pi in nature.

[Ag(MeL)(HMeL)(sub 2)](sub 2) and [Ag(PhL(HPhL)](sub 2) have resulted from the title azooximes PhNNC(R)NOH, HRL(R = Me, Ph). Strong H...H hydrogen bonds characterize the species while the Ag...Ag distances are shorter and longer than the van der Waals sum in [Ag(PhL(HPhL)](sub 2)and [Ag(MeL)(HMeL)(sub 2)](sub 2).

A scrutiny of the synthesis and structure of 2-(phenylazo) aniline (H2L) and bis chelate Pd II - (HL) sub 2, is presented. Structural studies indicate distortion in the phenyl ring adjacent to the chelate ring with two short and four long C-C distances.

Reports that azooximes PhNNC(R)NOH, HRL (R = Me,Ph) have afforded [Ag(MeL)(HMeL)2]2 (2) and [Ag(PhL)(HPhL)]2 (3). Coordination of only oxime N in compound 2; Distorted-T shape of the AgN3 fragment in compound 2; Chelating ligand in compound 3; Presence of strong O...O hydrogen bonds.