Reactions of 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol, HL [where H represents the dissociable phenolic protons of ligands and aryl groups of HL are C₆H₅ (HL¹), 𝑝-CH₃C₆H₅ (HL²), 𝑝-ClC₆H₅ (HL³)] with Os(H)(CO)(Br)(PPh₃)₃ in toluene and with Co(ClO₄)₃.6H₂O in methanol afforded new facially coordinated complexes of composition [(L)Os(CO)(Br)(PPh₃)] and [(L)₂Co]ClO₄. The anionic ligand (L)⁻, binds the metal in tridentate (N, N, O) manner in [(L)Os(CO)(Br)(PPh₃)] and [(L)₂Co]ClO₄ complexes. All the Os(II) and Co(III) complexes are diamagnetic and show characteristic ¹H NMR signals and intense MLCT transitions in the visible region. The cyclic voltammograms exhibited one quasi reversible oxidative response near 0.10 V vs SCE for [(L)Os(CO)(Br)(PPh₃)] and [(L)₂Co]ClO₄ complexes displayed serial reductive responses within −0.06 to −1.61 V vs SCE. Single point DFT calculation was carried out to examine the nature of redox orbitals. Conversion of ketones to corresponding alcohols has been studied using [(L)Os(CO)(Br)(PPh₃)] as catalyst.