A high-valent non heme μ-oxo MnIV dimer generated from a thiolate-bound MnII complex and O2

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

doi:10.1002/anie.201703215

A high-valent non heme μ-oxo MnIV dimer generated from a thiolate-bound MnII complex and O2

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

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Abstract

This study deals with the unprecedented reactivity of
dinuclear non heme Mn^II–thiolate complexes with O₂, 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 ¹⁸O₂
unambiguously shows that the oxygen atoms present in the Mn^IV
dimers originate from O₂. 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.

Original language	English
Journal	Angewandte Chemie - International Edition
Early online date	23 May 2017
DOIs	https://doi.org/10.1002/anie.201703215
Publication status	Published - 2017

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Manchester Institute of Biotechnology

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Duboc_et_al-2017-Angewandte_Chemie_International_EditionAccepted author manuscript, 4.39 MB

CCDC 1539856: Experimental Crystal Structure Determination
Brazzolotto, D. (Contributor), Cantu Reinhard, F. (Contributor), Smith-Jones, J. (Contributor), Retegan, M. (Contributor), Amidani, L. (Contributor), Faponle, A. (Contributor), Ray, K. (Contributor), Philouze, C. (Contributor), De Visser, S. (Contributor), Gennari, M. (Contributor) & Duboc, C. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1npbsg, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1npbsg&sid=DataCite
Dataset
CCDC 1539855: Experimental Crystal Structure Determination
Brazzolotto, D. (Contributor), Cantu Reinhard, F. (Contributor), Smith-Jones, J. (Contributor), Retegan, M. (Contributor), Amidani, L. (Contributor), Faponle, A. (Contributor), Ray, K. (Contributor), Philouze, C. (Contributor), De Visser, S. (Contributor), Gennari, M. (Contributor) & Duboc, C. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1npbrf, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1npbrf&sid=DataCite
Dataset

Cite this

@article{b272af53d7c64cb4ad63e33f36278eae,

title = "A high-valent non heme μ-oxo MnIV dimer generated from a thiolate-bound MnII complex and O2",

abstract = "This study deals with the unprecedented reactivity ofdinuclear non heme MnII–thiolate complexes with O2, whichdependent on the protonation state of the initial MnII dimerselectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo MnIVcomplex. Both dimers have been characterized by differenttechniques including single-crystal X-ray diffraction and massspectrometry. Oxygenation reactions carried out with labeled 18O2unambiguously shows that the oxygen atoms present in the MnIVdimers originate from O2. Based on experimental observations andDFT calculations, evidence is provided that these MnIV speciescomproportionate with a MnII precursor to yield μ-oxo and/or μ-hydroxo MnIII dimers. Our work highlights the delicate balance ofreaction conditions to control the synthesis of non heme high-valentμ-oxo and μ-hydroxo Mn species from MnII precursors and O2.",

author = "Deborah Brazzolotto and {Cantu Reinhard}, Fabian and Julian Smith-Jones and Marius Retegan and Lucia Amidani and Abayomi Faponle and Kallol Ray and Christian Philouze and {De Visser}, Samuel and Marcello Gennari and Carole Duboc",

year = "2017",

doi = "10.1002/anie.201703215",

language = "English",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons Ltd",

}

TY - JOUR

T1 - A high-valent non heme μ-oxo MnIV dimer generated from a thiolate-bound MnII complex and O2

AU - Brazzolotto, Deborah

AU - Cantu Reinhard, Fabian

AU - Smith-Jones, Julian

AU - Retegan, Marius

AU - Amidani, Lucia

AU - Faponle, Abayomi

AU - Ray, Kallol

AU - Philouze, Christian

AU - De Visser, Samuel

AU - Gennari, Marcello

AU - Duboc, Carole

PY - 2017

Y1 - 2017

N2 - This study deals with the unprecedented reactivity ofdinuclear non heme MnII–thiolate complexes with O2, whichdependent on the protonation state of the initial MnII dimerselectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo MnIVcomplex. Both dimers have been characterized by differenttechniques including single-crystal X-ray diffraction and massspectrometry. Oxygenation reactions carried out with labeled 18O2unambiguously shows that the oxygen atoms present in the MnIVdimers originate from O2. Based on experimental observations andDFT calculations, evidence is provided that these MnIV speciescomproportionate with a MnII precursor to yield μ-oxo and/or μ-hydroxo MnIII dimers. Our work highlights the delicate balance ofreaction conditions to control the synthesis of non heme high-valentμ-oxo and μ-hydroxo Mn species from MnII precursors and O2.

AB - This study deals with the unprecedented reactivity ofdinuclear non heme MnII–thiolate complexes with O2, whichdependent on the protonation state of the initial MnII dimerselectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo MnIVcomplex. Both dimers have been characterized by differenttechniques including single-crystal X-ray diffraction and massspectrometry. Oxygenation reactions carried out with labeled 18O2unambiguously shows that the oxygen atoms present in the MnIVdimers originate from O2. Based on experimental observations andDFT calculations, evidence is provided that these MnIV speciescomproportionate with a MnII precursor to yield μ-oxo and/or μ-hydroxo MnIII dimers. Our work highlights the delicate balance ofreaction conditions to control the synthesis of non heme high-valentμ-oxo and μ-hydroxo Mn species from MnII precursors and O2.

U2 - 10.1002/anie.201703215

DO - 10.1002/anie.201703215

M3 - Article

SN - 1433-7851

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

ER -

A high-valent non heme μ-oxo MnIV dimer generated from a thiolate-bound MnII complex and O2

Abstract

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CCDC 1539856: Experimental Crystal Structure Determination

CCDC 1539855: Experimental Crystal Structure Determination

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