A Mn(iv )–peroxo complex in the reactions with proton donors
| Autor: | Wonwoo Nam, Ming-Hsi Chiang, Chi He Chuo, Xiao Xi Li, Muniyandi Sankaralingam, Chien Ming Lee, Peter P.-Y. Chen, Yong Min Lee, Tzu Hsien Tseng |
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| Rok vydání: | 2019 |
| Předmět: | |
| Zdroj: | Dalton Transactions. 48:5203-5213 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/c9dt00649d |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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