A high‐valent non‐heme μ‐oxo manganese(IV) dimer generated from a thiolate‐bound manganese(II) complex and dioxygen
Résumé
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 O2 .
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