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

Autor: Brazzolotto D; Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000, Grenoble, France.; Univ. Grenoble Alpes, CNRS, UMR 5249, LCBM, 38000, Grenoble, France., Cantú Reinhard FG; Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK., Smith-Jones J; Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000, Grenoble, France., Retegan M; European Synchrotron Radiation Facility (ESRF), 71 Avenue des Martyrs, 38000, Grenoble, France., Amidani L; European Synchrotron Radiation Facility (ESRF), 71 Avenue des Martyrs, 38000, Grenoble, France., Faponle AS; Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK., Ray K; Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany., Philouze C; Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000, Grenoble, France., de Visser SP; Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK., Gennari M; Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000, Grenoble, France., Duboc C; Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000, Grenoble, France.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2017 Jul 03; Vol. 56 (28), pp. 8211-8215. Date of Electronic Publication: 2017 Jun 09.
DOI: 10.1002/anie.201703215
Abstrakt: 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 .
(© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
Externí odkaz: