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

Research output: Contribution to journalArticlepeer-review

7 Scopus citations


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 languageEnglish
Pages (from-to)5203-5213
Number of pages11
JournalDalton Transactions
Issue number16
StatePublished - 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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