A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Angewandte Chemie International Edition Année : 2017

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

Lucia Amidani

Résumé

This study deals with the unprecedented reactivity of dinuclear non-heme MnII -thiolate complexes with O2 , which dependent on the protonation state of the initial MnII dimer selectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo MnIV 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 O2 unambiguously show that the oxygen atoms present in the MnIV dimers originate from O2 . Based on experimental observations and DFT calculations, evidence is provided that these MnIV species comproportionate with a MnII precursor to yield μ-oxo and/or μ-hydroxo MnIII 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 MnII precursors and O2 .

Dates et versions

hal-02154187 , version 1 (12-06-2019)

Identifiants

Citer

Déborah Brazzolotto, Fabián G. Cantú reinhard, Julian Smith-Jones, Marius Retegan, Lucia Amidani, et al.. A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen. Angewandte Chemie International Edition, 2017, 56 (28), pp.8211-8215. ⟨10.1002/anie.201703215⟩. ⟨hal-02154187⟩
111 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More