• De Visser, Samuel P.
• Amidani, Lucia
• Faponle, Abayomi
• Duboc, Carole
• Retegan, Marius
• Smith-Jones, Julian
• Reinhard, Fabian Cantu
• Gennari, Marcello
• Brazzolotto, Deborah
• Philouze, Christian
• Ray, Kallol

Abstract

This study deals with the unprecedented reactivity of<br/>dinuclear non heme Mn^II–thiolate complexes with O₂, which<br/>dependent on the protonation state of the initial Mn^II dimer<br/>selectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo Mn^IV<br/>complex. Both dimers have been characterized by different<br/>techniques including single-crystal X-ray diffraction and mass<br/>spectrometry. Oxygenation reactions carried out with labeled ¹⁸O₂<br/>unambiguously shows that the oxygen atoms present in the Mn^IV<br/>dimers originate from O₂. Based on experimental observations and<br/>DFT calculations, evidence is provided that these Mn^IV species<br/>comproportionate with a Mn^II precursor to yield μ-oxo and/or μ-<br/>hydroxo Mn^III dimers. Our work highlights the delicate balance of<br/>reaction conditions to control the synthesis of non heme high-valent<br/>μ-oxo and μ-hydroxo Mn species from Mn^II precursors and O₂.

Topics

• impedance spectroscopy
• x-ray diffraction
• Oxygen
• density functional theory
• spectrometry