O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex

Claire Deville; Sandeep K.  Padamati; Jonas Sundberg; Vickie McKee; Wesley R. Browne; Christine McKenzie

doi:10.1002/anie.201508372

O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex

Claire Deville, Sandeep K. Padamati, Jonas Sundberg, Vickie McKee, Wesley R. Browne, Christine McKenzie

Institut for Fysik, Kemi og Farmaci

University of Groningen

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

Abstract

A Mn ^II complex, [Mn(dpeo) ₂] ²⁺ (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O ₂, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn ^III complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn ^II complex of the final ketone ligand, cis-[MnBr ₂(hidpe) ₂] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H ₂ ¹⁸O and ¹⁸O ₂ labeling experiments suggest that the inserted O atoms originate from two different O ₂ molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit.

Originalsprog	Engelsk
Tidsskrift	Angewandte Chemie International Edition
Vol/bind	55
Udgave nummer	2
Sider (fra-til)	545-549
ISSN	1433-7851
DOI	https://doi.org/10.1002/anie.201508372
Status	Udgivet - jan. 2016

Dokumenter og links

10.1002/anie.201508372

http://onlinelibrary.wiley.com/doi/10.1002/ange.201508372/pdf

Syddansk Universitet
Deville, C. (Gæsteunderviser)
11. mar. 2015 → 19. mar. 2015
Aktivitet: Gæsteophold ved andre institutioner

Harnessing the oxidising power of air
Deville, C. & McKenzie, C. J.
25/01/2016
1 element af Mediedækning
Presse/medie

Citationsformater

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title = "O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex",

abstract = "A Mn II complex, [Mn(dpeo) 2] 2+ (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O 2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn III complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn II complex of the final ketone ligand, cis-[MnBr 2(hidpe) 2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H 2 18O and 18O 2 labeling experiments suggest that the inserted O atoms originate from two different O 2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit. ",

keywords = "C-H oxidation, O activation, catalysis, manganese, oxime ligands",

author = "Claire Deville and Padamati, {Sandeep K.} and Jonas Sundberg and Vickie McKee and Browne, {Wesley R.} and Christine McKenzie",

year = "2016",

month = jan,

doi = "10.1002/anie.201508372",

language = "English",

volume = "55",

pages = "545--549",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "Wiley",

number = "2",

}

TY - JOUR

T1 - O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex

AU - Deville, Claire

AU - Padamati, Sandeep K.

AU - Sundberg, Jonas

AU - McKee, Vickie

AU - Browne, Wesley R.

AU - McKenzie, Christine

PY - 2016/1

Y1 - 2016/1

N2 - A Mn II complex, [Mn(dpeo) 2] 2+ (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O 2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn III complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn II complex of the final ketone ligand, cis-[MnBr 2(hidpe) 2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H 2 18O and 18O 2 labeling experiments suggest that the inserted O atoms originate from two different O 2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit.

AB - A Mn II complex, [Mn(dpeo) 2] 2+ (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O 2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn III complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn II complex of the final ketone ligand, cis-[MnBr 2(hidpe) 2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H 2 18O and 18O 2 labeling experiments suggest that the inserted O atoms originate from two different O 2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit.

KW - C-H oxidation

KW - O activation

KW - catalysis

KW - manganese

KW - oxime ligands

U2 - 10.1002/anie.201508372

DO - 10.1002/anie.201508372

M3 - Journal article

SN - 1433-7851

VL - 55

SP - 545

EP - 549

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 2

ER -

O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex

Abstract

Dokumenter og links

Fingeraftryk

Relaterede aktiviteter

Syddansk Universitet

Relateret presse/medie

Harnessing the oxidising power of air

Citationsformater