eprintid: 10193378
rev_number: 8
eprint_status: archive
userid: 699
dir: disk0/10/19/33/78
datestamp: 2024-06-13 11:21:33
lastmod: 2025-02-04 07:10:07
status_changed: 2024-06-13 11:21:33
type: article
metadata_visibility: show
sword_depositor: 699
creators_name: Wilson, Daniel WN
creators_name: Fataftah, Majed S
creators_name: Mathe, Zachary
creators_name: Mercado, Brandon Q
creators_name: DeBeer, Serena
creators_name: Holland, Patrick L
title: Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster
ispublished: pub
divisions: UCL
divisions: B04
divisions: C06
divisions: F56
note: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
abstract: Biological multielectron reactions often are performed by metalloenzymes with heterometallic sites, such as anaerobic carbon monoxide dehydrogenase (CODH), which has a nickel–iron–sulfide cubane with a possible three-coordinate nickel site. Here, we isolate the first synthetic iron–sulfur clusters having a nickel atom with only three donors, showing that this structural feature is feasible. These have a core with two tetrahedral irons, one octahedral tungsten, and a three-coordinate nickel connected by sulfide and thiolate bridges. Electron paramagnetic resonance (EPR), Mössbauer, and superconducting quantum interference device (SQUID) data are combined with density functional theory (DFT) computations to show how the electronic structure of the cluster arises from strong magnetic coupling between the Ni, Fe, and W sites. X-ray absorption spectroscopy, together with spectroscopically validated DFT analysis, suggests that the electronic structure can be described with a formal Ni1+ atom participating in a nonpolar Ni–W σ-bond. This metal–metal bond, which minimizes spin density at Ni1+, is conserved in two cluster oxidation states. Fe–W bonding is found in all clusters, in one case stabilizing a local non-Hund state at tungsten. Based on these results, we compare different M–M interactions and speculate that other heterometallic clusters, including metalloenzyme active sites, could likewise store redox equivalents and stabilize low-valent metal centers through metal–metal bonding.
date: 2024-02-14
date_type: published
publisher: American Chemical Society
official_url: http://dx.doi.org/10.1021/jacs.3c12157
oa_status: green
full_text_type: other
language: eng
primo: open
primo_central: open_green
verified: verified_manual
elements_id: 2283703
doi: 10.1021/jacs.3c12157
lyricists_name: Wilson, Daniel
lyricists_id: DWILS16
actors_name: Wilson, Daniel
actors_id: DWILS16
actors_role: owner
funding_acknowledgements: [National Institute of General Medical Sciences]; GM-065313 [Max Planck Society]; F32-GM136179 [Max Planck Society]; DE 1877/1-2 [National Institutes of Health]; DE-AC02-76SF00515 [Deutsche Forschungsgemeinschaft]; [U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences]
full_text_status: public
publication: Journal of the American Chemical Society
volume: 146
number: 6
pagerange: 4013-4025
pages: 13
issn: 0002-7863
citation:        Wilson, Daniel WN;    Fataftah, Majed S;    Mathe, Zachary;    Mercado, Brandon Q;    DeBeer, Serena;    Holland, Patrick L;      (2024)    Three-Coordinate Nickel and Metal–Metal Interactions in a Heterometallic Iron–Sulfur Cluster.                   Journal of the American Chemical Society , 146  (6)   pp. 4013-4025.    10.1021/jacs.3c12157 <https://doi.org/10.1021/jacs.3c12157>.       Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/10193378/1/proof-2%20%281%29.pdf