Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles | |
Department | OSSO国家重点实验室 |
Guo, Mian1; Yong-Min Lee1; Ranjana Gupta1; Mi Sook Seo1; Takehiro Ohta2; Wang, Hua-Hua3; Liu, Hai-Yang3; Sunder N. Dhuri1,4; Ritimukta Sarangi5; Shunichi Fukuzumi1; Wonwoo Nam1,6 | |
2017 | |
Source Publication | Journal of the American Chemical Society |
ISSN | 0002-7863 |
Volume | 139Issue:44Pages:15858-15867 |
Abstract | Activation of dioxygen (O2) in enzymatic and biomimetic reactions has been intensively investigated over the past several decades. More recently, O–O bond formation, which is the reverse of the O2-activation reaction, has been the focus of current research. Herein, we report the O2-activation and O–O bond formation reactions by manganese corrole complexes. In the O2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O2 in the presence of base (e.g., OH–) and hydrogen atom (H atom) donor (e.g., THF or cyclic olefins); the O2-activation reaction did not occur in the absence of base and H atom donor. Moreover, formation of the Mn(V)-oxo and Mn(IV)-peroxo species was dependent on the amounts of base present in the reaction solution. The role of the base was proposed to lower the oxidation potential of the Mn(III) corroles, thereby facilitating the binding of O2 and forming a Mn(IV)-superoxo species. The putative Mn(IV)-superoxo species was then converted to the corresponding Mn(IV)-hydroperoxo species by abstracting a H atom from H atom donor, followed by the O–O bond cleavage of the putative Mn(IV)-hydroperoxo species to form a Mn(V)-oxo species. We have also shown that addition of hydroxide ion to the Mn(V)-oxo species afforded the Mn(IV)-peroxo species via O–O bond formation and the resulting Mn(IV)-peroxo species reverted to the Mn(V)-oxo species upon addition of proton, indicating that the O–O bond formation and cleavage reactions between the Mn(V)-oxo and Mn(IV)-peroxo complexes are reversible. The present study reports the first example of using the same manganese complex in both O2-activation and O–O bond formation reactions. |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1021/jacs.7b08678 |
Funding Organization | the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.);GRL (NRF-2010-00353 to W.N.);Basic Science Research Program ( 2017R1D1A1B03029982 t o Y . - M . L .;2017R1D1A1B03032615 to S.F.);a Grant-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), a SENTAN project from the Japan Science and Technology Agency (JST) to S.F.;National Natural Science Foundation of China (No. 21371059;No. 21671068);The SSRL SMB resource was supported by the NIH National Institute of General Medical Sciences (NIGMS) through a Biomedical Technology Research Resource P41 grant (P41GM103393) and by the DOE Office of Biological and Environmental Research |
Indexed By | SCI |
If | 13.858 |
Language | 英语 |
compositor | 第六作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/22769 |
Collection | 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Ritimukta Sarangi; Shunichi Fukuzumi; Wonwoo Nam |
Affiliation | 1.Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea 2.Univ Hyogo, Picobiol Inst, Grad Sch Life Sci, RSC UH LP Ctr, Mikazuki, Hyogo 6795148, Japan 3.South China Univ Technol, Dept Chem, Guangzhou 510641, Guangdong, Peoples R China 4.Goa Univ, Dept Chem, Taleigao 403206, Goa, India 5.SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA 6.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Gansu, Peoples R China |
Recommended Citation GB/T 7714 | Guo, Mian,Yong-Min Lee,Ranjana Gupta,et al. Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles[J]. Journal of the American Chemical Society,2017,139(44):15858-15867. |
APA | Guo, Mian.,Yong-Min Lee.,Ranjana Gupta.,Mi Sook Seo.,Takehiro Ohta.,...&Wonwoo Nam.(2017).Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles.Journal of the American Chemical Society,139(44),15858-15867. |
MLA | Guo, Mian,et al."Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles".Journal of the American Chemical Society 139.44(2017):15858-15867. |
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