We present a theoretical extension of the previously published bicarbonate hydrogenation to formate and formic acid dehydrogenation catalysed by FeII complexes bearing the linear tetraphosphine ligand tetraphos-1. The hydrogenation reaction was found to proceed at the singlet surface with two competing pathways: A) H2 association to the Fe-H species followed by deprotonation to give a Fe(H)2 intermediate, which then reacts with CO2 to give formate. B) CO2 insertion into the Fe-H bond, followed by H2 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)(H2), which undergoes extremely rapid hydrogen exchange.
Mechanistic Studies on NaHCO3 Hydrogenation and HCOOH Dehydrogenation Reactions Catalysed by a FeII Linear Tetraphosphine Complex
Bertini F;Peruzzini M;Gonsalvi L;
2018
Abstract
We present a theoretical extension of the previously published bicarbonate hydrogenation to formate and formic acid dehydrogenation catalysed by FeII complexes bearing the linear tetraphosphine ligand tetraphos-1. The hydrogenation reaction was found to proceed at the singlet surface with two competing pathways: A) H2 association to the Fe-H species followed by deprotonation to give a Fe(H)2 intermediate, which then reacts with CO2 to give formate. B) CO2 insertion into the Fe-H bond, followed by H2 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)(H2), which undergoes extremely rapid hydrogen exchange.| File | Dimensione | Formato | |
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prod_383355-doc_130685.pdf
Open Access dal 15/12/2018
Descrizione: "This is the peer reviewed version of the following article: R. Marcos, F. Bertini, Z. Rinkevicius, M. Peruzzini, L. Gonsalvi, M. S. G. Ahlquist, Chem. Eur. J. 2018, 24, 5366, which has been published in final form at https://doi.org/10.1002/chem.201704927. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited."
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