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

doi:10.1002/chem.201902100

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

Uppsala University

Research output: Contribution to journal › Article › peer-review

3 Citations (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 language	English
Pages (from-to)	11135-11140
Number of pages	6
Journal	Chemistry - A European Journal
Volume	25
Issue number	47
DOIs	https://doi.org/10.1002/chem.201902100
Publication status	Published - Aug 22 2019

Keywords

IR spectroscopy
biomimetic catalysts
hydrogen
iron
reaction intermediates

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.201902100

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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, Vol. 25, No. 47, 22.08.2019, p. 11135-11140.

Research output: Contribution to journal › Article › peer-review

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

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.",

keywords = "IR spectroscopy, biomimetic catalysts, hydrogen, iron, reaction intermediates",

author = "Shihuai Wang and Sonja Pullen and Valentin Weippert and Tianfei Liu and Sascha Ott and Reiner Lomoth and Leif Hammarstr{\"o}m",

note = "Funding Information: This work was supported by the Swedish Research Council (grant no. 2016-04271) and the Foundation Olle Engkvist Byggm?stare (granted 2016/3). S.W. gratefully acknowledges a grant from the Chinese Scholarship Council. Funding Information: This work was supported by the Swedish Research Council (grant no. 2016‐04271) and the Foundation Olle Engkvist Byggm{\"a}stare (granted 2016/3). S.W. gratefully acknowledges a grant from the Chinese Scholarship Council. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Liu, Tianfei

AU - Ott, Sascha

AU - Lomoth, Reiner

AU - Hammarström, Leif

N1 - Funding Information: This work was supported by the Swedish Research Council (grant no. 2016-04271) and the Foundation Olle Engkvist Byggm?stare (granted 2016/3). S.W. gratefully acknowledges a grant from the Chinese Scholarship Council. Funding Information: This work was supported by the Swedish Research Council (grant no. 2016‐04271) and the Foundation Olle Engkvist Byggmästare (granted 2016/3). S.W. gratefully acknowledges a grant from the Chinese Scholarship Council. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/8/22

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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 - biomimetic catalysts

KW - hydrogen

KW - iron

KW - reaction intermediates

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