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 journal › Article

1 Citation (Scopus)

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 journal › Article

Wang, S, Pullen, S, Weippert, V, Liu, T, Ott, S, Lomoth, R & Hammarström, L 2019, 'Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst', Chemistry - A European Journal. https://doi.org/10.1002/chem.201902100
Wang S, Pullen S, Weippert V, Liu T, Ott S, Lomoth R et al. Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst. Chemistry - A European Journal. 2019 Jan 1. https://doi.org/10.1002/chem.201902100
Wang, Shihuai ; Pullen, Sonja ; Weippert, Valentin ; Liu, Tianfei ; Ott, Sascha ; Lomoth, Reiner ; Hammarström, Leif. / Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst. In: Chemistry - A European Journal. 2019.
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AU - Wang, Shihuai

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 - hydrogen

KW - IR spectroscopy

KW - iron

KW - reaction intermediates

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