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 -