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

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [4]; ORCiD logo [2];  [5];  [3]; ORCiD logo [2];  [3]; ORCiD logo [3]
  1. Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000 Grenoble France, Univ. Grenoble Alpes, CNRS, UMR 5249, LCBM, 38000 Grenoble France
  2. Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street Manchester M1 7DN UK
  3. Univ. Grenoble Alpes, CNRS, UMR 5250, DCM, 38000 Grenoble France
  4. European Synchrotron Radiation Facility (ESRF), 71 Avenue des Martyrs 38000 Grenoble France
  5. Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2 12489 Berlin Germany
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401308
Grant/Contract Number:
AC02-76SF00515
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 28; Related Information: CHORUS Timestamp: 2017-10-20 16:30:31; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Brazzolotto, Deborah, Cantú Reinhard, Fabián G., Smith-Jones, Julian, Retegan, Marius, Amidani, Lucia, Faponle, Abayomi S., Ray, Kallol, Philouze, Christian, de Visser, Sam P., Gennari, Marcello, and Duboc, Carole. A High-Valent Non-Heme μ-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen. Germany: N. p., 2017. Web. doi:10.1002/ange.201703215.
Brazzolotto, Deborah, Cantú Reinhard, Fabián G., Smith-Jones, Julian, Retegan, Marius, Amidani, Lucia, Faponle, Abayomi S., Ray, Kallol, Philouze, Christian, de Visser, Sam P., Gennari, Marcello, & Duboc, Carole. A High-Valent Non-Heme μ-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen. Germany. doi:10.1002/ange.201703215.
Brazzolotto, Deborah, Cantú Reinhard, Fabián G., Smith-Jones, Julian, Retegan, Marius, Amidani, Lucia, Faponle, Abayomi S., Ray, Kallol, Philouze, Christian, de Visser, Sam P., Gennari, Marcello, and Duboc, Carole. Fri . "A High-Valent Non-Heme μ-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen". Germany. doi:10.1002/ange.201703215.
@article{osti_1401308,
title = {A High-Valent Non-Heme μ-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen},
author = {Brazzolotto, Deborah and Cantú Reinhard, Fabián G. and Smith-Jones, Julian and Retegan, Marius and Amidani, Lucia and Faponle, Abayomi S. and Ray, Kallol and Philouze, Christian and de Visser, Sam P. and Gennari, Marcello and Duboc, Carole},
abstractNote = {},
doi = {10.1002/ange.201703215},
journal = {Angewandte Chemie},
number = 28,
volume = 129,
place = {Germany},
year = {Fri Jun 09 00:00:00 EDT 2017},
month = {Fri Jun 09 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 9, 2018
Publisher's Accepted Manuscript

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  • Cited by 3
  • A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of ~4.4 in the oxidation of para-substituted thioanisoles.
  • Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N 5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc 3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–Hmore » bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.« less
  • The tetranuclear species [Mn[sup IV] [sub 4]O[sub 6] (bpy)[sub 6]] (ClO[sub 4])[sub 4][center dot]H[sub 2]O was isolated from an aqueous nitric acid solution (pH = 2) of Mn[sup III] (bpy) Cl[sub 3](H[sub 2]O) upon addition of NaClO[sub 4]. It crystallizes in the triclinic space group P[bar l] with a = 20.213(7) [angstrom], b = 13.533(7) [angstrom], c = 13.411(8) [angstrom], [alpha] = 112.01(8)[degree], [beta] = 96.72(11)[degree], [gamma] = 100.34(12)[degree], V = 3276.9 [angstrom][sup 3], and Z = 2. The cation has a nonrectilinear chain structure [(bpy)[sub 2]Mn[sup IV[sub a]]O[sub 2]Mn[sup IV[sub b]](bpy)O[sub 2]Mn[sup IV[sub c]](bpy)O[sub 2]Mn[sup IV[sub d]](bpy)[sub 2]][sup 4+].more » The metal-metal distances are Mn[sub a]-Mn[sub b] = 2.746(5) [angstrom], Mn[sub b]-Mn[sub c] = 2.760(5) [angstrom], Mn[sub c]-Mn[sub d] = 2.735(4) [angstrom], Mn[sub a]-Mn[sub c] = 4.899(10) [angstrom], Mn[sub b]-Mn[sub d] = 4.897(6) [angstrom], and Mn[sub a]-Mn[sub d] = 6.419(11) [angstrom]. The variable temperature magnetic susceptibility data for [Mn[sup IV[sub 4]]O[sub 6](bpy)[sub 6]](ClO[sub 4])[sub 4][center dot]H[sub 2]O in the range 12-294 K were fit using the spin Hamiltonian H[sub S] = J[sub ab]S[sub a]S[sub b] -J[sub bc]S[sub b]S[sub c] - J[sub cd]S[sub c]S[sub d], with J[sub ab] = J[sub cd] = -176 cm[sup [minus]1] and J[sub bc] = [minus]268 cm[sup [minus]1]. 55 refs., 11 figs., 3 tabs.« less