High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites

Anna G. Scott; Diogo Alves Galico; Isabel Bogacz; Paul H. Oyala; Junko Yano; Elizaveta A. Suturina; Muralee Murugesu; Theodor Agapie

doi:10.1002/anie.202313880

High-Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

Anna G. Scott, Diogo Alves Galico, Isabel Bogacz, Paul H. Oyala, Junko Yano, Elizaveta A. Suturina, Muralee Murugesu, Theodor Agapie

Research output: Contribution to journal › Article › peer-review

7 Citations (SciVal)

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Abstract

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*₄W₄Fe₁₃S₁₂, displaying a Fe₁₃ core with M−M bonds that has precedent only in main group and late metal chemistry. M₁₃ clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*₄W₄Fe₁₃S₁₂ displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

Original language	English
Article number	e202313880
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	49
Early online date	23 Oct 2023
DOIs	https://doi.org/10.1002/anie.202313880
Publication status	Published - 4 Dec 2023

Funding

We are grateful to the National Institutes of Health (R01‐GM102687B to T.A.) and the National Science Foundation (Graduate Research Fellowships Program to A.G.S.) for funding, the Beckman Institute and the Dow Next Generation Grant for instrumentation support, Michael Takase and Lawrence Henling for assistance with crystallography. Part of this work (XAS data collection) was carried out at the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515. XAS studies were performed with support of the NIH GM110501 (J.Y.). EAS gratefully acknowledges the University of Bath's Research Computing Group (doi.org/10.15125/b6cd‐s854) for their support in this work.

Keywords

High-Spin
Iron-Sulfur Clusters
Magnetic Properties
Metal-Metal Interactions
Small Molecule Activation

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.202313880

Fe13Manuscript_Revised_AGS_8-6-2023_1_TA_ES
This is the peer reviewed version of the following article: Angew. Chem.Int. Ed.2023,62, e20231388, which has been published in final form at https://doi.org/10.1002/anie.202313880. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Accepted author manuscript, 1.37 MB

Cite this

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abstract = "Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12, displaying a Fe13 core with M−M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.",

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