Jump to main content
Jump to site search

Issue 16, 2019
Previous Article Next Article

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

Author affiliations

Abstract

Protons play an important role in promoting O–O or M–O bond cleavage of metal–peroxo complexes. Treatment of side-on O2-bound [PPN][MnIV(TMSPS3)(O2)] (1, PPN = bis(triphenylphosphine)iminium and TMSPS3H3 = 2,2′,2′′-trimercapto-3,3′,3′′-tris(trimethylsilyl)triphenylphosphine) with perchloric acid (HClO4) in the presence of PR3 (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate MnIII(OPR3)(TMSPS3) 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 MnIV–peroxo complex, leading to the isolation of a series of five-coordinate [MnIII(L)(TMSPS3)] complexes (L = phenylthiolate, phenolate or methoxide). Mechanistic aspects of the reactions of the MnIV–peroxo complex with proton donors are discussed as well.

Graphical abstract: A Mn(iv)–peroxo complex in the reactions with proton donors

Back to tab navigation

Supplementary files

Article information


Submitted
13 Feb 2019
Accepted
18 Mar 2019
First published
19 Mar 2019

Dalton Trans., 2019,48, 5203-5213
Article type
Paper

A Mn(IV)–peroxo complex in the reactions with proton donors

C. Lee, M. Sankaralingam, C. Chuo, T. Tseng, P. P.-Y. Chen, M. Chiang, X. Li, Y. Lee and W. Nam, Dalton Trans., 2019, 48, 5203
DOI: 10.1039/C9DT00649D

Social activity

Search articles by author

Spotlight

Advertisements