A Mn(iv)-peroxo complex in the reactions with proton donors

Chien Ming Lee; Muniyandi Sankaralingam; Chi He Chuo; Tzu Hsien Tseng; Peter P.Y. Chen; Ming Hsi Chiang; Xiao Xi Li; Yong Min Lee; Wonwoo Nam

doi:10.1039/c9dt00649d

A Mn(iv)-peroxo complex in the reactions with proton donors

Chien Ming Lee, Muniyandi Sankaralingam, Chi He Chuo, Tzu Hsien Tseng, Peter P.Y. Chen, Ming Hsi Chiang, Xiao Xi Li, Yong Min Lee, Wonwoo Nam

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Protons play an important role in promoting O-O or M-O bond cleavage of metal-peroxo complexes. Treatment of side-on O ₂ -bound [PPN][Mn ^IV ( ^TMS PS3)(O ₂ )] (1, PPN = bis(triphenylphosphine)iminium and ^TMS PS3H ₃ = 2,2′,2′′-trimercapto-3,3′,3′′-tris(trimethylsilyl)triphenylphosphine) with perchloric acid (HClO ₄ ) in the presence of PR ₃ (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate Mn ^III (OPR ₃ )( ^TMS PS3) complexes (R = phenyl, 2a; p-tolyl, 2b), which are confirmed by X-ray crystallography. Isotope labelling experiments demonstrate that the oxygen atom in the phosphine oxide product derives from the peroxo ligand of 1. Reactions of 1 with weak proton donors, such as phenylthiol, phenol, substituted phenol and methanol, are also investigated to explore the reactivity of the Mn ^IV -peroxo complex, leading to the isolation of a series of five-coordinate [Mn ^III (L)( ^TMS PS3)] ⁻ complexes (L = phenylthiolate, phenolate or methoxide). Mechanistic aspects of the reactions of the Mn ^IV -peroxo complex with proton donors are discussed as well.

Original language	English
Pages (from-to)	5203-5213
Number of pages	11
Journal	Dalton Transactions
Volume	48
Issue number	16
DOIs	https://doi.org/10.1039/c9dt00649d
State	Published - 2019

Bibliographical note

Funding Information:
C.-M. Lee thanks Dr Gene-Hsiang Lee (Instrumentation Center, National Taiwan University, Taiwan) for collection of X-ray diffraction data and the support from the Ministry of Science and Technology of Taiwan (Grant 105-2113-M-143-001). This work was also supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W. N.), GRL (NRF-2010-00353 to W. N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M. L.).

Publisher Copyright:
© The Royal Society of Chemistry.

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@article{b5d709214aa246a59df6e07392304be9,

title = "A Mn(iv)-peroxo complex in the reactions with proton donors",

abstract = " Protons play an important role in promoting O-O or M-O bond cleavage of metal-peroxo complexes. Treatment of side-on O 2 -bound [PPN][Mn IV ( TMS PS3)(O 2 )] (1, PPN = bis(triphenylphosphine)iminium and TMS PS3H 3 = 2,2′,2′′-trimercapto-3,3′,3′′-tris(trimethylsilyl)triphenylphosphine) with perchloric acid (HClO 4 ) in the presence of PR 3 (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate Mn III (OPR 3 )( TMS PS3) complexes (R = phenyl, 2a; p-tolyl, 2b), which are confirmed by X-ray crystallography. Isotope labelling experiments demonstrate that the oxygen atom in the phosphine oxide product derives from the peroxo ligand of 1. Reactions of 1 with weak proton donors, such as phenylthiol, phenol, substituted phenol and methanol, are also investigated to explore the reactivity of the Mn IV -peroxo complex, leading to the isolation of a series of five-coordinate [Mn III (L)( TMS PS3)] − complexes (L = phenylthiolate, phenolate or methoxide). Mechanistic aspects of the reactions of the Mn IV -peroxo complex with proton donors are discussed as well. ",

author = "Lee, {Chien Ming} and Muniyandi Sankaralingam and Chuo, {Chi He} and Tseng, {Tzu Hsien} and Chen, {Peter P.Y.} and Chiang, {Ming Hsi} and Li, {Xiao Xi} and Lee, {Yong Min} and Wonwoo Nam",

note = "Funding Information: C.-M. Lee thanks Dr Gene-Hsiang Lee (Instrumentation Center, National Taiwan University, Taiwan) for collection of X-ray diffraction data and the support from the Ministry of Science and Technology of Taiwan (Grant 105-2113-M-143-001). This work was also supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W. N.), GRL (NRF-2010-00353 to W. N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M. L.). Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9dt00649d",

language = "English",

volume = "48",

pages = "5203--5213",

journal = "Dalton Transactions",

issn = "1477-9226",

number = "16",

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TY - JOUR

T1 - A Mn(iv)-peroxo complex in the reactions with proton donors

AU - Lee, Chien Ming

AU - Sankaralingam, Muniyandi

AU - Chuo, Chi He

AU - Tseng, Tzu Hsien

AU - Chen, Peter P.Y.

AU - Chiang, Ming Hsi

AU - Li, Xiao Xi

AU - Lee, Yong Min

AU - Nam, Wonwoo

N1 - Funding Information: C.-M. Lee thanks Dr Gene-Hsiang Lee (Instrumentation Center, National Taiwan University, Taiwan) for collection of X-ray diffraction data and the support from the Ministry of Science and Technology of Taiwan (Grant 105-2113-M-143-001). This work was also supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W. N.), GRL (NRF-2010-00353 to W. N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M. L.). Publisher Copyright: © The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - Protons play an important role in promoting O-O or M-O bond cleavage of metal-peroxo complexes. Treatment of side-on O 2 -bound [PPN][Mn IV ( TMS PS3)(O 2 )] (1, PPN = bis(triphenylphosphine)iminium and TMS PS3H 3 = 2,2′,2′′-trimercapto-3,3′,3′′-tris(trimethylsilyl)triphenylphosphine) with perchloric acid (HClO 4 ) in the presence of PR 3 (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate Mn III (OPR 3 )( TMS PS3) complexes (R = phenyl, 2a; p-tolyl, 2b), which are confirmed by X-ray crystallography. Isotope labelling experiments demonstrate that the oxygen atom in the phosphine oxide product derives from the peroxo ligand of 1. Reactions of 1 with weak proton donors, such as phenylthiol, phenol, substituted phenol and methanol, are also investigated to explore the reactivity of the Mn IV -peroxo complex, leading to the isolation of a series of five-coordinate [Mn III (L)( TMS PS3)] − complexes (L = phenylthiolate, phenolate or methoxide). Mechanistic aspects of the reactions of the Mn IV -peroxo complex with proton donors are discussed as well.

AB - Protons play an important role in promoting O-O or M-O bond cleavage of metal-peroxo complexes. Treatment of side-on O 2 -bound [PPN][Mn IV ( TMS PS3)(O 2 )] (1, PPN = bis(triphenylphosphine)iminium and TMS PS3H 3 = 2,2′,2′′-trimercapto-3,3′,3′′-tris(trimethylsilyl)triphenylphosphine) with perchloric acid (HClO 4 ) in the presence of PR 3 (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate Mn III (OPR 3 )( TMS PS3) complexes (R = phenyl, 2a; p-tolyl, 2b), which are confirmed by X-ray crystallography. Isotope labelling experiments demonstrate that the oxygen atom in the phosphine oxide product derives from the peroxo ligand of 1. Reactions of 1 with weak proton donors, such as phenylthiol, phenol, substituted phenol and methanol, are also investigated to explore the reactivity of the Mn IV -peroxo complex, leading to the isolation of a series of five-coordinate [Mn III (L)( TMS PS3)] − complexes (L = phenylthiolate, phenolate or methoxide). Mechanistic aspects of the reactions of the Mn IV -peroxo complex with proton donors are discussed as well.

UR - http://www.scopus.com/inward/record.url?scp=85064565469&partnerID=8YFLogxK

U2 - 10.1039/c9dt00649d

DO - 10.1039/c9dt00649d

M3 - Article

C2 - 30941378

AN - SCOPUS:85064565469

SN - 1477-9226

VL - 48

SP - 5203

EP - 5213

JO - Dalton Transactions

JF - Dalton Transactions

IS - 16

ER -

A Mn(iv)-peroxo complex in the reactions with proton donors

Abstract

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