Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst

Shihuai Wang, Sonja Pullen, Valentin Weippert, Tianfei Liu, Sascha Ott, Reiner Lomoth, Leif Hammarström

Research output: Contribution to journalArticle

Abstract

[FeFe(Cl2-bdt)(CO)6] (1; Cl2-bdt=3,6-dichlorobenzene-1,2-dithiolate), inspired by the active site of FeFe-hydrogenase, shows a chemically reversible 2 e reduction at −1.20 V versus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reduction potential and stabilizes the reduced forms, compared with analogous complexes with aliphatic dithiolates; thus allowing details of the catalytic process to be characterized. Herein, time-resolved IR spectroscopy is used to provide kinetic and structural information on key catalytic intermediates. This includes the doubly reduced, protonated complex 1H, which has not been previously identified experimentally. In addition, the first direct spectroscopic observation of the turnover process for a molecular H2 evolving catalyst is reported, allowing for straightforward determination of the turnover frequency.

Original languageEnglish
JournalChemistry - A European Journal
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Biomimetics
Hydrogenase
Catalysts
Carbon Monoxide
Infrared spectroscopy
Ligands
Kinetics
ferrocenium
ferrocene
2-dichlorobenzene

Keywords

  • biomimetic catalysts
  • hydrogen
  • IR spectroscopy
  • iron
  • reaction intermediates

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst. / Wang, Shihuai; Pullen, Sonja; Weippert, Valentin; Liu, Tianfei; Ott, Sascha; Lomoth, Reiner; Hammarström, Leif.

In: Chemistry - A European Journal, 01.01.2019.

Research output: Contribution to journalArticle

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AU - Pullen, Sonja

AU - Weippert, Valentin

AU - Liu, Tianfei

AU - Ott, Sascha

AU - Lomoth, Reiner

AU - Hammarström, Leif

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N2 - [FeFe(Cl2-bdt)(CO)6] (1; Cl2-bdt=3,6-dichlorobenzene-1,2-dithiolate), inspired by the active site of FeFe-hydrogenase, shows a chemically reversible 2 e− reduction at −1.20 V versus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reduction potential and stabilizes the reduced forms, compared with analogous complexes with aliphatic dithiolates; thus allowing details of the catalytic process to be characterized. Herein, time-resolved IR spectroscopy is used to provide kinetic and structural information on key catalytic intermediates. This includes the doubly reduced, protonated complex 1H−, which has not been previously identified experimentally. In addition, the first direct spectroscopic observation of the turnover process for a molecular H2 evolving catalyst is reported, allowing for straightforward determination of the turnover frequency.

AB - [FeFe(Cl2-bdt)(CO)6] (1; Cl2-bdt=3,6-dichlorobenzene-1,2-dithiolate), inspired by the active site of FeFe-hydrogenase, shows a chemically reversible 2 e− reduction at −1.20 V versus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reduction potential and stabilizes the reduced forms, compared with analogous complexes with aliphatic dithiolates; thus allowing details of the catalytic process to be characterized. Herein, time-resolved IR spectroscopy is used to provide kinetic and structural information on key catalytic intermediates. This includes the doubly reduced, protonated complex 1H−, which has not been previously identified experimentally. In addition, the first direct spectroscopic observation of the turnover process for a molecular H2 evolving catalyst is reported, allowing for straightforward determination of the turnover frequency.

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KW - IR spectroscopy

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