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Title: Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase

Abstract

Hydrogenases couple electrochemical potential to the reversible chemical transformation of H2 and protons, yet the reaction mechanism and composition of intermediates are not fully understood. In this Communication we describe the biophysical properties of a hydride-bound state (Hhyd) of the [FeFe]-hydrogenase from Chlamydomonas reinhardtii. The catalytic H-cluster of [FeFe]-hydrogenase consists of a [4Fe-4S] subcluster ([4Fe-4S]H) linked by a cysteine thiol to an azadithiolate-bridged 2Fe subcluster ([2Fe]H) with CO and CN- ligands. Mossbauer analysis and density functional theory (DFT) calculations show that Hhyd consists of a reduced [4Fe-4S]H+ coupled to a diferrous [2Fe]H with a terminally bound Fe-hydride. The existence of the Fe-hydride in Hhyd was demonstrated by an unusually low Mossbauer isomer shift of the distal Fe of the [2Fe]H subcluster. As a result, a DFT model of Hhyd shows that the Fe-hydride is part of a H-bonding network with the nearby bridging azadithiolate to facilitate fast proton exchange and catalytic turnover.

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Carnegie Mellon Univ., Pittsburgh, PA (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1340645
Report Number(s):
NREL/JA-2700-67578
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 1; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chlamydomonas reinhardtii; [FeFe]-hydrogenase; electrochemical potential

Citation Formats

Mulder, David W., Guo, Yisong, Ratzloff, Michael W., and King, Paul W.. Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase. United States: N. p., 2016. Web. https://doi.org/10.1021/jacs.6b11409.
Mulder, David W., Guo, Yisong, Ratzloff, Michael W., & King, Paul W.. Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase. United States. https://doi.org/10.1021/jacs.6b11409
Mulder, David W., Guo, Yisong, Ratzloff, Michael W., and King, Paul W.. Wed . "Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase". United States. https://doi.org/10.1021/jacs.6b11409. https://www.osti.gov/servlets/purl/1340645.
@article{osti_1340645,
title = {Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase},
author = {Mulder, David W. and Guo, Yisong and Ratzloff, Michael W. and King, Paul W.},
abstractNote = {Hydrogenases couple electrochemical potential to the reversible chemical transformation of H2 and protons, yet the reaction mechanism and composition of intermediates are not fully understood. In this Communication we describe the biophysical properties of a hydride-bound state (Hhyd) of the [FeFe]-hydrogenase from Chlamydomonas reinhardtii. The catalytic H-cluster of [FeFe]-hydrogenase consists of a [4Fe-4S] subcluster ([4Fe-4S]H) linked by a cysteine thiol to an azadithiolate-bridged 2Fe subcluster ([2Fe]H) with CO and CN- ligands. Mossbauer analysis and density functional theory (DFT) calculations show that Hhyd consists of a reduced [4Fe-4S]H+ coupled to a diferrous [2Fe]H with a terminally bound Fe-hydride. The existence of the Fe-hydride in Hhyd was demonstrated by an unusually low Mossbauer isomer shift of the distal Fe of the [2Fe]H subcluster. As a result, a DFT model of Hhyd shows that the Fe-hydride is part of a H-bonding network with the nearby bridging azadithiolate to facilitate fast proton exchange and catalytic turnover.},
doi = {10.1021/jacs.6b11409},
journal = {Journal of the American Chemical Society},
number = 1,
volume = 139,
place = {United States},
year = {2016},
month = {12}
}

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