Abstract
[FeFe]-hydrogenases feature a unique active site in which the primary catalytic unit is directly coordinated via a bridging cysteine thiolate to a secondary, redox active [4Fe4S] unit. The goal of this study was to evaluate the impact of a bidentate, redox non-innocent ligand on the electrocatalytic properties of the (μ-S(CH2)3S)Fe2(CO) 4L2 family of [FeFe]-hydrogenase models as a proxy for the iron-sulfur cluster. Reaction of the redox non-innocent ligand 2,2′-bipyridyl (bpy) with (μ-S(CH2)3S)Fe 2(CO)6 leads to substitution of two carbonyls to form the asymmetric complex (μ-S(CH2)3S)Fe2(CO) 4(κ2-bpy) which was structurally characterized by single crystal X-ray crystallography. This complex can be protonated by HBF 4·OEt2 to form a bridging hydride. Furthermore, electrochemical investigation shows that, at slow scan rates, the complex undergoes a two electron reduction at -2.06 V vs. Fc+/Fc that likely involves reduction of both the bpy ligand and the metal. Electrocatalytic reduction of protons is observed in the presence of three distinct acids of varying strengths: HBF4·OEt2, AcOH, and p-TsOH. The catalytic mechanism depends on the strength of the acid.
| Original language | English |
|---|---|
| Pages (from-to) | 3843-3853 |
| Number of pages | 11 |
| Journal | Dalton Transactions |
| Volume | 42 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Mar 21 2013 |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Biomimetic model for [FeFe]-hydrogenase : Asymmetrically disubstituted diiron complex with a redox-active 2,2′-bipyridyl ligand. / Roy, Souvik; Groy, Thomas L.; Jones, Anne Katherine.
In: Dalton Transactions, Vol. 42, No. 11, 21.03.2013, p. 3843-3853.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Biomimetic model for [FeFe]-hydrogenase
T2 - Asymmetrically disubstituted diiron complex with a redox-active 2,2′-bipyridyl ligand
AU - Roy, Souvik
AU - Groy, Thomas L.
AU - Jones, Anne Katherine
PY - 2013/3/21
Y1 - 2013/3/21
N2 - [FeFe]-hydrogenases feature a unique active site in which the primary catalytic unit is directly coordinated via a bridging cysteine thiolate to a secondary, redox active [4Fe4S] unit. The goal of this study was to evaluate the impact of a bidentate, redox non-innocent ligand on the electrocatalytic properties of the (μ-S(CH2)3S)Fe2(CO) 4L2 family of [FeFe]-hydrogenase models as a proxy for the iron-sulfur cluster. Reaction of the redox non-innocent ligand 2,2′-bipyridyl (bpy) with (μ-S(CH2)3S)Fe 2(CO)6 leads to substitution of two carbonyls to form the asymmetric complex (μ-S(CH2)3S)Fe2(CO) 4(κ2-bpy) which was structurally characterized by single crystal X-ray crystallography. This complex can be protonated by HBF 4·OEt2 to form a bridging hydride. Furthermore, electrochemical investigation shows that, at slow scan rates, the complex undergoes a two electron reduction at -2.06 V vs. Fc+/Fc that likely involves reduction of both the bpy ligand and the metal. Electrocatalytic reduction of protons is observed in the presence of three distinct acids of varying strengths: HBF4·OEt2, AcOH, and p-TsOH. The catalytic mechanism depends on the strength of the acid.
AB - [FeFe]-hydrogenases feature a unique active site in which the primary catalytic unit is directly coordinated via a bridging cysteine thiolate to a secondary, redox active [4Fe4S] unit. The goal of this study was to evaluate the impact of a bidentate, redox non-innocent ligand on the electrocatalytic properties of the (μ-S(CH2)3S)Fe2(CO) 4L2 family of [FeFe]-hydrogenase models as a proxy for the iron-sulfur cluster. Reaction of the redox non-innocent ligand 2,2′-bipyridyl (bpy) with (μ-S(CH2)3S)Fe 2(CO)6 leads to substitution of two carbonyls to form the asymmetric complex (μ-S(CH2)3S)Fe2(CO) 4(κ2-bpy) which was structurally characterized by single crystal X-ray crystallography. This complex can be protonated by HBF 4·OEt2 to form a bridging hydride. Furthermore, electrochemical investigation shows that, at slow scan rates, the complex undergoes a two electron reduction at -2.06 V vs. Fc+/Fc that likely involves reduction of both the bpy ligand and the metal. Electrocatalytic reduction of protons is observed in the presence of three distinct acids of varying strengths: HBF4·OEt2, AcOH, and p-TsOH. The catalytic mechanism depends on the strength of the acid.
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UR - http://www.scopus.com/inward/citedby.url?scp=84874096258&partnerID=8YFLogxK
U2 - 10.1039/c2dt32457a
DO - 10.1039/c2dt32457a
M3 - Article
VL - 42
SP - 3843
EP - 3853
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 11
ER -