A Mn(iv)-peroxo complex in the reactions with proton donors
- 주제(기타) Chemistry, Inorganic & Nuclear
- 설명문(일반) [Lee, Chien-Ming; Chuo, Chi-He] Natl Taitung Univ, Dept Appl Sci, Jhihben Campus 369,Sec 2,Univ Rd, Taitung 950, Taiwan; [Sankaralingam, Muniyandi; Li, Xiao-Xi; Lee, Yong-Min; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Sankaralingam, Muniyandi] Natl Inst Technol Calicut, Dept Chem, Calicut 673601, Kerala, India; [Tseng, Tzu-Hsien; Chen, Peter P. -Y.] Natl Chung Hsing Univ, Dept Chem, 145 Xingda Rd, Taichung 402, Taiwan; [Chiang, Ming-Hsi] Acad Sinica, Inst Chem, 128 Acad Rd,Sec 2, Taipei 11529, Taiwan
- 등재 SCIE, SCOPUS
- 발행기관 ROYAL SOC CHEMISTRY
- 발행년도 2019
- URI http://www.dcollection.net/handler/ewha/000000159688
- 본문언어 영어
- Published As http://dx.doi.org/10.1039/c9dt00649d
- PubMed https://pubmed.ncbi.nlm.nih.gov/30941378
초록/요약
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 (HClO4) in the presence of PR3 (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate Mn-III(OPR3)((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.
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