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