title: Exclusively Ligand-Mediated Catalytic Dehydrogenation of Alcohols.
abstract: 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 kH/kDisotope effect of 12.2 ± 0.1 at 300 K. A hydrogenated intermediate compound, [NiIICl2(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.
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Debabrata
authors.initials: D
authors.lastname: Sengupta
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Rameswar
authors.initials: R
authors.lastname: Bhattacharjee
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Rajib
authors.initials: R
authors.lastname: Pramanick
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Santi Prasad
authors.initials: SP
authors.lastname: Rath
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Nabanita
authors.initials: N
authors.lastname: Saha Chowdhury
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Ayan
authors.initials: A
authors.lastname: Datta
authors.affiliation: Department of Inorganic Chemistry and ΔDepartment of Spectroscopy, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032, India.
authors.forename: Sreebrata
authors.initials: S
authors.lastname: Goswami
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000447:Aldehydes / Q000138:chemical synthesis; D001391:Azo Compounds / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D006865:Hydrogenation; D007659:Ketones / Q000138:chemical synthesis; D008024:Ligands; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry; D010084:Oxidation-Reduction; D011789:Quantum Theory
chemical_list: D000438:Alcohols; D000447:Aldehydes; D001391:Azo Compounds; D056831:Coordination Complexes; D007659:Ketones; D008024:Ligands; D009532:Nickel