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 |
|---|---|
| Journal | Chemistry - A European Journal |
| DOIs | |
| Publication status | Published - Jan 1 2019 |
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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
}
TY - JOUR
T1 - Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst
AU - Wang, Shihuai
AU - Pullen, Sonja
AU - Weippert, Valentin
AU - Liu, Tianfei
AU - Ott, Sascha
AU - Lomoth, Reiner
AU - Hammarström, Leif
PY - 2019/1/1
Y1 - 2019/1/1
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.
KW - biomimetic catalysts
KW - hydrogen
KW - IR spectroscopy
KW - iron
KW - reaction intermediates
UR - http://www.scopus.com/inward/record.url?scp=85070101491&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85070101491&partnerID=8YFLogxK
U2 - 10.1002/chem.201902100
DO - 10.1002/chem.201902100
M3 - Article
AN - SCOPUS:85070101491
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
ER -