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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b11409· OSTI ID:1340645
 [1];  [2];  [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Carnegie Mellon Univ., Pittsburgh, PA (United States)
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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.

Research Organization:
NREL (National Renewable Energy Laboratory (NREL), Golden, CO (United States))
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1340645
Report Number(s):
NREL/JA--2700-67578
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 1 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (21)

In Vivo EPR Characterization of Semi-Synthetic [FeFe] Hydrogenases journal February 2018
1H NMR Spectroscopy of [FeFe] Hydrogenase: Insight into the Electronic Structure of the Active Site journal December 2017
Spectroscopic and Computational Evidence that [FeFe] Hydrogenases Operate Exclusively with CO-Bridged Intermediates journal December 2019
A [4Fe–4S]-Fe(CO)(CN)-l-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly journal April 2018
From protein engineering to artificial enzymes – biological and biomimetic approaches towards sustainable hydrogen production journal January 2018
A [RuRu] Analogue of an [FeFe]-Hydrogenase Traps the Key Hydride Intermediate of the Catalytic Cycle journal March 2018
In Vivo EPR Characterization of Semi-Synthetic [FeFe] Hydrogenases journal February 2018
A [RuRu] Analogue of an [FeFe]-Hydrogenase Traps the Key Hydride Intermediate of the Catalytic Cycle journal March 2018
Direct Noncovalent Activation of α,β-Unsaturated Aldehydes for the Stereodivergent Synthesis of Substituted Cyclohexenes journal April 2017
Accumulating the hydride state in the catalytic cycle of [FeFe]-hydrogenases journal July 2017
Crystallographic and spectroscopic assignment of the proton transfer pathway in [FeFe]-hydrogenases journal November 2018
The plasticity of redox cofactors: from metalloenzymes to redox-active DNA journal August 2018
Protonation/reduction dynamics at the [4Fe–4S] cluster of the hydrogen-forming cofactor in [FeFe]-hydrogenases journal January 2018
DFT methods applied to answer the question: how accurate is the ligand acidity constant method for estimating the p K a of transition metal hydride complexes MHXL 4 when X is varied? journal January 2018
Chalcogenide substitution in the [2Fe] cluster of [FeFe]-hydrogenases conserves high enzymatic activity journal January 2017
A coordinatively saturated nickel complex supported by triazenido ligands: a new electrocatalyst for hydrogen generation via ligand-centered proton-transfer journal January 2017
[FeFe]-Hydrogenases: recent developments and future perspectives journal January 2018
Recent advances in the mechanisms of the hydrogen evolution reaction by non-innocent sulfur-coordinating metal complexes journal January 2020
Serine is the molecular source of the NH(CH 2 ) 2 bridgehead moiety of the in vitro assembled [FeFe] hydrogenase H-cluster journal January 2020
The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor journal September 2019
[FeFe]-Hydrogenases: recent developments and future perspectives text January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chlamydomonas reinhardtii
[FeFe]-hydrogenase
electrochemical potential