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Mechanistic Studies on NaHCO 3 Hydrogenation and HCOOH Dehydrogenation Reactions Catalysed by a Fe II Linear Tetraphosphine Complex
Author(s) -
Marcos Rocío,
Bertini Federica,
Rinkevicius Zilvinas,
Peruzzini Maurizio,
Gonsalvi Luca,
Ahlquist Mårten S. G.
Publication year - 2018
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.201704927
Subject(s) - dehydrogenation , deprotonation , formic acid , chemistry , formate , medicinal chemistry , ligand (biochemistry) , singlet state , hydrogen , photochemistry , methyl formate , inorganic chemistry , catalysis , organic chemistry , ion , biochemistry , physics , receptor , nuclear physics , excited state
We present a theoretical extension of the previously published bicarbonate hydrogenation to formate and formic acid dehydrogenation catalysed by Fe II complexes bearing the linear tetraphosphine ligand tetraphos‐1. The hydrogenation reaction was found to proceed at the singlet surface with two competing pathways: A) H 2 association to the Fe−H species followed by deprotonation to give a Fe(H) 2 intermediate, which then reacts with CO 2 to give formate. B) CO 2 insertion into the Fe−H bond, followed by H 2 association and subsequent deprotonation. B was found to be slightly preferred with an activation energy of 22.8 kcal mol −1 , compared to 25.3 for A. Further we have reassigned the Fe−H complex, as a Fe(H)(H 2 ), which undergoes extremely rapid hydrogen exchange.