Theoretical studies of [FeFe]-hydrogenase: infrared fingerprints of the dithiol-bridging ligand in the active site.

Full Abstract

An unresolved structural issue for [FeFe]-hydrogenases is the nature of the dithiol-bridging ligand in the diiron subcluster of the active site. The two most probable candidates are 1,3-dithiopropane (propane dithiol, PDT) and di-(thiomethyl)-amine (DTN). In the latter case, the dithiol-bridging ligand is assumed to play a major role in the reaction cycle. We report density-functional theory studies of the differing roles of these dithiol-bridging ligands in the infrared spectra of synthetic models and of computational representations of the diiron cluster of the active site. Our analysis shows distinct spectral features associated with the dithiol-bridging NH mode for compounds having a DTN bridge, which, however, would have been obscured by the H2O vibrations in existing measurements. However, if indeed nitrogen is present in the dithiol-bridging ligand, a combination of selective deuteration and chemical inactivation with CO would create a unique signature in an accessible region of the infrared spectrum, whose position and intensity are predicted.

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Author information

Author/s: Zilberman, Silviu (S); Stiefel, Edward I (EI); Cohen, Morrel H (MH); Car, Roberto (R);

Affiliation: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA. silviu(-atsign-)princeton.edu

Journal and publication information

Publication Type: Journal Article; Research Support, Non-U.S. Gov't

Journal: Inorganic chemistry (Inorg Chem), published in United States. (Language: eng)

Reference: 2007-Feb; vol 46 (issue 4) : pp 1153-61

Dates: Created 2007/02/12; Completed 2007/04/05;

PMID: 17256840, status: MEDLINE (last retrieval date: 12/26/2008)

Sourced from the National Library of Medicine. Abstract text and other information may be subject to copyright.

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MeSH headings (categories)

This article was linked to the MESH Headings shown below.

Binding Sites
Carbon Monoxide - chemistry
Diamines - chemistry
Hydrogen - chemistry
Hydrogenase - chemistry
Iron - chemistry
Iron-Sulfur Proteins - chemistry
Ligands

Models, Theoretical
Molecular Structure
Nitrogen - chemistry
Propane - analogs & derivatives
Spectrophotometry, Infrared - methods
Toluene - analogs & derivatives; chemistry
Triazenes - chemistry
Water - chemistry

Associated Chemicals: Diamines (0) ; Iron-Sulfur Proteins (0) ; Ligands (0) ; Triazenes (0) ; Toluene (108-88-3) ; Hydrogen (1333-74-0) ; dithiol (496-74-2) ; Carbon Monoxide (630-08-0) ; 1-phenyl-3,3-dimethyltriazene (7227-91-0) ; Propane (74-98-6) ; Iron (7439-89-6) ; Nitrogen (7727-37-9) ; Water (7732-18-5) ; iron hydrogenase (EC 1.12.-) ; Hydrogenase (EC 1.18.99.1)

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