Design of an efficient new catalyst that can mimic the enzymatic pathway for catalytic dehydrogenation of liquid fuels like alcohols is described in this report. The catalyst is a nickel(II) complex of 2,6-bis(phenylazo)pyridine ligand (L); which possesses the above requisite with excellent catalytic efficiencies for controlled dehydrogenation of alcohols using ligand-based redox couple. Mechanistic studies supported by density functional theory calculations revealed that the catalytic cycle involves hydrogen atom transfer via quantum mechanical tunneling with significant k(H)/k(D) isotope effect of 12.2 +/- 0.1 at 300 K A hydrogenated intermediate compound, [(NiCL2)-C-II(H2L)], is isolated and characterized. The results are promising in the context of design of cheap and efficient earth-abundant metal catalyst for alcohol oxidation and hydrogen storage.