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Computational Study of Formic Acid Dehydrogenation Catalyzed by Al III –Bis(imino)pyridine
Author(s) -
Lu QianQian,
Yu HaiZhu,
Fu Yao
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504573
Subject(s) - dehydrogenation , chemistry , pyridine , formic acid , catalysis , protonation , catalytic cycle , medicinal chemistry , imine , hydride , bond cleavage , photochemistry , ligand (biochemistry) , inorganic chemistry , organic chemistry , hydrogen , biochemistry , receptor , ion
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 CO 2 , and the formed ( H,H PDI)Al(OOCH) 2 H mediates HCOOH to release H 2 .