Can Manganese(III)-Iodosylarene Act as an Oxidant Alongside High-Valent Manganese(V)-Oxo Complexes? | |
Department | OSSO国家重点实验室 |
Kang, Yiran1,2; Wang F(王芳)1; Fabián G. Cantú Reinhard3,4; Xia CG(夏春谷)1; Sam P. de Visse3,4; Wang Y(王永)1; Wang Y(王永) | |
The second department | osso国家重点实验室 |
2018 | |
Source Publication | ChemistrySelect |
ISSN | 2365-6549 |
Volume | 3Issue:11Pages:3208-3213 |
Abstract | Metalloenzymes often utilize a high‐valent metal‐oxo species in their catalytic cycle that is formed through a combination of reduction/proton transfer steps from O2. In biomimetic chemistry, by contrast, the use of molecular oxygen is challenging and instead addition of iodosylarenes as terminal oxidants generates these high‐valent metal‐oxo intermediates. There has been controversy in the literature for many years, whether the iodosylarene (or one of its side‐products in a reaction with a metal center) can act as an active oxidant. Herein, we present a comprehensive theoretical study on the thioanisole oxidation by a range of possible oxidants originating from a reaction mixture of a Mn(III) complex with iodosylbenzene. We show here that actually there are multiple isomeric iodosylarene complexes in solution and a number of those react with substrates with rate‐determining barriers at par with high‐valent metal‐oxo species. In particular, the [MnIII(PhIO)], [MnV(O)(PhIO)] and [MnIV(O)‐I(Ph)‐O•] complexes are identified as competitive oxidants and as such care should be taken with interpreting experimental rate constants. |
Keyword | Biomimetic Models Manganese Nonheme Reactivity Sulfoxidation |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1002/slct.201800678 |
Funding Organization | National Natural Science Foundation of China (grants 21003116 ; 21173211) |
Indexed By | SCI |
If | 1.505 |
Language | 英语 |
Funding Project | 均相催化研究组 |
compositor | 第一作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/23639 |
Collection | 苏州研究院 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Sam P. de Visse; Wang Y(王永) |
Affiliation | 1.Chinese Acad Sci, LICP, Suzhou Res Inst, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Gansu, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 3.Univ Manchester, Manchester Inst Biotechnol, 131 Princess St, Manchester M1 7DN, Lancs, England 4.Univ Manchester, Sch Chem Engn & Analyt Sci, 131 Princess St, Manchester M1 7DN, Lancs, England |
Recommended Citation GB/T 7714 | Kang, Yiran,Wang F,Fabián G. Cantú Reinhard,et al. Can Manganese(III)-Iodosylarene Act as an Oxidant Alongside High-Valent Manganese(V)-Oxo Complexes?[J]. ChemistrySelect,2018,3(11):3208-3213. |
APA | Kang, Yiran.,Wang F.,Fabián G. Cantú Reinhard.,Xia CG.,Sam P. de Visse.,...&Wang Y.(2018).Can Manganese(III)-Iodosylarene Act as an Oxidant Alongside High-Valent Manganese(V)-Oxo Complexes?.ChemistrySelect,3(11),3208-3213. |
MLA | Kang, Yiran,et al."Can Manganese(III)-Iodosylarene Act as an Oxidant Alongside High-Valent Manganese(V)-Oxo Complexes?".ChemistrySelect 3.11(2018):3208-3213. |
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1528159731337.pdf(4090KB) | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text |
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