Herein, we communicate the formation of novel ruthenium compounds with N, X-donor (X=O, N) heterocyclic-derived ligands. A paramagnetic ruthenium(IV) complex, [RuCl(pho)(bzca)(PPh 3 )](1) (pho=2-aminophenolate; bzca=2-carboxylate-1H-benzimidazole) was isolated from the reaction of the ruthenium(II) precursor, trans-[RuCl 2 (PPh 3 ) 3 ] and 2-((1H-benzimidazole)methylamino)phenol (Hbzap). The 1:1 molar reaction between the same metal precursor and N-(benzoxazole)-2-hydroxybenzamide (H 2 bhb) led to the formation of cis-Cl, trans-P-[Ru III (Hbhb)Cl 2 (PPh 3 ) 2 ](2). The dinuclear ruthenium compounds, (μ-Htba,Cl) 2 [Ru II Cl(PPh 3 )] 2 (3) (Htba=N-(thiophene)methyl-benzoxazole-2-amine) and (μ-Cl) 2 [Ru III Cl(Hchpr)(PPh 3 )] 2 (4) (H 2 chpr=2-amino-3-((tetrahydro-2H-pyran-4-ylimino)methyl)-4H-chromen-4-one) were formed from the equimolar ratio coordination reactions between trans-[RuCl 2 (PPh 3 ) 3 ] and the respective free-ligands, Htba and H 2 chpr. These metal complexes were characterized via IR-, NMR- and UV–Vis spectroscopy, molar conductivity measurements and structural elucidations were confirmed by single crystal X-ray analysis. The X-ray studies revealed that all the metallic compounds exhibited octahedral geometries and that the Hbzap free ligand has undergone a unique molecular transformation to afford the pho and bzca bidentate chelators in 1. The electrochemical properties of the respective metal complexes were investigated by voltammetric analysis. The cyclic voltammograms (CVs) of 1–3 showed one redox couple while within the CV of the dinuclear compound 4, two redox couples were observed. The ligands and their metal complexes were also subjected to DPPH radical scavenging studies. The IC 50 values showed that all the metallic compounds have higher radical scavenging activities than their corresponding free-ligands and the natural antioxidant, Vitamin C.