English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Planar three-coordinate iron sulfide in a synthetic [4Fe-3S] cluster with biomimetic reactivity

DeRosha, D. E., Chilkuri, V. G., Van Stappen, C., Bill, E., Mercado, B. Q., DeBeer, S., et al. (2019). Planar three-coordinate iron sulfide in a synthetic [4Fe-3S] cluster with biomimetic reactivity. Nature Chemistry, 11(11), 1019-1025. doi:10.1038/s41557-019-0341-7.

Item is

Files

show Files

Locators

show

Creators

show
hide
 Creators:
DeRosha, Daniel E.1, Author
Chilkuri, Vijay G.2, Author           
Van Stappen, Casey3, Author
Bill, Eckhard3, Author
Mercado, Brandon Q.1, Author
DeBeer, Serena4, Author           
Neese, Frank2, Author           
Holland, Patrick L.1, Author
Affiliations:
1Department of Chemistry, Yale University, New Haven, CT, USA, ou_persistent22              
2Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
3Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany, ou_persistent22              
4Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              

Content

show
hide
Free keywords: -
 Abstract: Iron–sulfur clusters are emerging as reactive sites for the reduction of small-molecule substrates. However, the four-coordinate iron sites of typical iron–sulfur clusters rarely react with substrates, implicating three-coordinate iron. This idea is untested because fully sulfide-coordinated three-coordinate iron is unprecedented. Here we report a new type of [4Fe-3S] cluster that features an iron centre with three bonds to sulfides, and characterize examples of the cluster in three oxidation levels using crystallography, spectroscopy, and ab initio calculations. Although a high-spin electronic configuration is characteristic of other iron–sulfur clusters, the three-coordinate iron centre in these clusters has a surprising low-spin electronic configuration due to the planar geometry and short Fe-S bonds. In a demonstration of biomimetic reactivity, the [4Fe-3S] cluster reduces hydrazine, a natural substrate of nitrogenase. The product is the first example of NH2 bound to an iron–sulfur cluster. Our results demonstrate that three-coordinate iron supported by sulfide donors is a plausible precursor to reactivity in iron–sulfur clusters like the FeMoco of nitrogenase.

Details

show
hide
Language(s): eng - English
 Dates: 2019-01-152019-08-192019-10-142019-11-01
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1038/s41557-019-0341-7
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Nature Chemistry
  Abbreviation : Nat. Chem.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: London, UK : Nature Publishing Group
Pages: - Volume / Issue: 11 (11) Sequence Number: - Start / End Page: 1019 - 1025 Identifier: ISSN: 1755-4330
CoNE: https://pure.mpg.de/cone/journals/resource/1755-4330