A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen

Brazzolotto, Deborah; Cantú Reinhard, Fabián G.; Smith‐Jones, Julian; Retegan, Marius; Amidani, Lucia; Faponle, Abayomi S.; Ray, Kallol; Philouze, Christian; de Visser, Sam P.; Gennari, Marcello; Duboc, Carole

doi:10.1002/anie.201703215

A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen

Journal Article · Fri Jun 09 00:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201703215· OSTI ID:1401557

Brazzolotto, Deborah ^[1]; ^[2]; Smith‐Jones, Julian ^[3]; ^[4]; Amidani, Lucia ^[4]; ^[2]; Ray, Kallol ^[5]; Philouze, Christian ^[3]; ^[2]; Gennari, Marcello ^[3]; ^[3]

Univ. Grenoble Alpes, CNRS, UMR 5250, DCM 38000 Grenoble France, Univ. Grenoble Alpes, CNRS, UMR 5249, LCBM 38000 Grenoble France
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science The University of Manchester 131 Princess Street Manchester M1 7DN UK
Univ. Grenoble Alpes, CNRS, UMR 5250, DCM 38000 Grenoble France
European Synchrotron Radiation Facility (ESRF) 71 Avenue des Martyrs 38000 Grenoble France
Department of Chemistry Humboldt-Universität zu Berlin Brook-Taylor-Strasse 2 12489 Berlin Germany

Abstract

This study deals with the unprecedented reactivity of dinuclear non‐heme Mn ^II –thiolate complexes with O ₂ , which dependent on the protonation state of the initial Mn ^II dimer selectively generates either a di‐μ‐oxo or μ‐oxo‐μ‐hydroxo Mn ^IV complex. Both dimers have been characterized by different techniques including single‐crystal X‐ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled ¹⁸ O ₂ unambiguously show that the oxygen atoms present in the Mn ^IV dimers originate from O ₂ . Based on experimental observations and DFT calculations, evidence is provided that these Mn ^IV species comproportionate with a Mn ^II precursor to yield μ‐oxo and/or μ‐hydroxo Mn ^III dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non‐heme high‐valent μ‐oxo and μ‐hydroxo Mn species from Mn ^II precursors and O ₂ .

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1401557

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 28 Vol. 56; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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