Detail publikačního výsledku

Hydrogenation of CO2 to methanol by the diphosphine-ruthenium(ii) cationic complex: a DFT investigation to shed light on the decisive role of carboxylic acids as promoters

BUTERA, V.; DETZ, H.

Originální název

Hydrogenation of CO2 to methanol by the diphosphine-ruthenium(ii) cationic complex: a DFT investigation to shed light on the decisive role of carboxylic acids as promoters

Anglický název

Hydrogenation of CO2 to methanol by the diphosphine-ruthenium(ii) cationic complex: a DFT investigation to shed light on the decisive role of carboxylic acids as promoters

Druh

Článek WoS

Originální abstrakt

In order to provide alternative paths for the CO2 conversion processes, we present a quantum-chemical investigation of the CO2 hydrogenation to methanol catalyzed by the recently proposed diphosphine-ruthenium(ii) cationic complex, named Ru2, in presence of carboxylic acids. Our results have shown that, in absence of carboxylate anion, CO2 molecule is not activated towards the hydride nucleophilic attack and, consequently, its hydrogenation does not occur. On the other hand, the addition of carboxylic acid 1) allows the replacement of the p-cymene ligand and, therefore, the formation of the active metal-carboxylate specie proposed experimentally, and 2) activates the CO2 molecule, thus confirming the experimental suggestion that carboxylic acid acts as promoter. Moreover, the influence of the size of the carbon chain in the carboxylate acid has been also investigated and rationalized. Eventually, DFT calculations have been carried out to explore the experimentally proposed catalytic cycle for the CO2 hydrogenation to methanol.

Anglický abstrakt

In order to provide alternative paths for the CO2 conversion processes, we present a quantum-chemical investigation of the CO2 hydrogenation to methanol catalyzed by the recently proposed diphosphine-ruthenium(ii) cationic complex, named Ru2, in presence of carboxylic acids. Our results have shown that, in absence of carboxylate anion, CO2 molecule is not activated towards the hydride nucleophilic attack and, consequently, its hydrogenation does not occur. On the other hand, the addition of carboxylic acid 1) allows the replacement of the p-cymene ligand and, therefore, the formation of the active metal-carboxylate specie proposed experimentally, and 2) activates the CO2 molecule, thus confirming the experimental suggestion that carboxylic acid acts as promoter. Moreover, the influence of the size of the carbon chain in the carboxylate acid has been also investigated and rationalized. Eventually, DFT calculations have been carried out to explore the experimentally proposed catalytic cycle for the CO2 hydrogenation to methanol.

Klíčová slova

CO2 conversion processes, quantum-chemical investigation

Klíčová slova v angličtině

CO2 conversion processes, quantum-chemical investigation

Autoři

BUTERA, V.; DETZ, H.

Rok RIV

2021

Vydáno

21.05.2021

Nakladatel

ROYAL SOC CHEMISTRY

Místo

CAMBRIDGE

ISSN

2044-4761

Periodikum

Catalysis Science & Technology

Svazek

11

Číslo

10

Stát

Spojené království Velké Británie a Severního Irska

Strany od

3556

Strany do

3567

Strany počet

12

URL

https://pubs.rsc.org/en/content/articlelanding/2021/CY/D1CY00502B#!divAbstract

BibTex

@article{BUT171906,
  author="Valeria {Butera} and Hermann {Detz}",
  title="Hydrogenation of CO2 to methanol by the diphosphine-ruthenium(ii) cationic complex: a DFT investigation to shed light on the decisive role of carboxylic acids as promoters",
  journal="Catalysis Science & Technology",
  year="2021",
  volume="11",
  number="10",
  pages="3556--3567",
  doi="10.1039/d1cy00502b",
  issn="2044-4753",
  url="https://pubs.rsc.org/en/content/articlelanding/2021/CY/D1CY00502B#!divAbstract"
}