title: Computational Study of Formic Acid Dehydrogenation Catalyzed by Al(III)-Bis(imino)pyridine.
abstract: The mechanism of formic acid dehydrogenation catalyzed by the bis(imino)pyridine-ligated aluminum hydride complex (PDI(2-))Al(THF)H (PDI=bis(imino)pyridine) was studied by density functional theory calculations. The overall transformation is composed of two stages: catalyst activation and the catalytic cycle. The catalyst activation begins with O-H bond cleavage of HCOOH promoted by aluminum-ligand cooperation, followed by HCOOH-assisted Al-H bond cleavage, and protonation of the imine carbon atom of the bis(imino)pyridine ligand. The resultant doubly protonated complex ((H,H) PDI)Al(OOCH)3 is the active catalyst for formic acid dehydrogenation. Given this, the catalytic cycle includes β-hydride elimination of ((H,H) PDI)Al(OOCH)3 to produce CO2, and the formed ((H,H) PDI)Al(OOCH)2 H mediates HCOOH to release H2.
authors.affiliation: Collaborative Innovation Centre of Chemistry for Energy Materials, CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
authors.forename: Qian-Qian
authors.initials: QQ
authors.lastname: Lu
authors.affiliation: Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui University, Hefei, 230601. yuhaizhu@ahu.edu.cn.
authors.forename: Hai-Zhu
authors.initials: HZ
authors.lastname: Yu
authors.affiliation: Collaborative Innovation Centre of Chemistry for Energy Materials, CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China. fuyao@ustc.edu.cn.
authors.forename: Yao
authors.initials: Y
authors.lastname: Fu
mesh_terms: D002384:Catalysis; D005561:Formates / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: C000611493:Al(III)-bis(imino)pyridine; D005561:Formates; D009942:Organometallic Compounds; D011725:Pyridines; C030544:formic acid
keywords: O−H bond activation; aluminum; density functional theory; formic acid dehydrogenation; redox non-innocent ligands