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

8 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",

publisher = "Royal Society of Chemistry",

number = "16",

}

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 - https://www.scopus.com/pages/publications/85064565469

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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