Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 남원우 | * |
dc.contributor.author | Shunichi Fukuzumi | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2022-07-14T16:31:04Z | - |
dc.date.available | 2022-07-14T16:31:04Z | - |
dc.date.issued | 2022 | * |
dc.identifier.issn | 0020-1669 | * |
dc.identifier.other | OAK-31634 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/261540 | - |
dc.description.abstract | Acids are known to enhance the reactivities of metal-oxygen intermediates, such as metal-oxo, -hydroperoxo, -peroxo, and -superoxo complexes, in biomimetic oxidation reactions. Although metal-aqua (and metal-hydroxo) complexes have been shown to be potent oxidants in oxidation reactions, acid effects on the reactivities of metal-aqua complexes have never been investigated previously. In this study, a mononuclear manganese(III)-aqua complex, [(dpaq5NO2)MnIII(OH2)]2+ (1; dpaq5NO2 = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-ylacetamidate with an NO2 substituent at the 5 position), which is relatively stable in the presence of triflic acid (HOTf), is used in the investigation of acid-catalyzed oxidation reactions by metal-aqua complexes. As a result, we report a remarkable acid catalysis in the six-electron oxidation of anthracene by 1 in the presence of HOTf; anthraquinone is formed as the product. In the HOTf-catalyzed six-electron oxidation of anthracene by 1, the rate constant increases linearly with an increase of the HOTf concentration. Combined with the observed one-electron oxidation product, anthracene (derivative) radical cation, and the substitution effect at the 5 position of the dpaq ligand in 1 on the rate constants of the oxidation of anthracene, it is concluded that the oxidation of anthracene occurs via an acid-promoted electron transfer (APET) from anthracene to 1. The dependence of the rate constants of the APET from electron donors, including anthracene derivatives, to 1 on the driving force of electron transfer is also shown to be well fitted by the Marcus equation of outer-sphere electron transfer. To the best of our knowledge, this is the first example showing acid catalysis in the oxidation of substrates by metal(III)-aqua complexes. © 2022 American Chemical Society. | * |
dc.language | English | * |
dc.publisher | American Chemical Society | * |
dc.title | Acid Catalysis in the Oxidation of Substrates by Mononuclear Manganese(III)-Aqua Complexes | * |
dc.type | Article | * |
dc.relation.issue | 17 | * |
dc.relation.volume | 61 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 6594 | * |
dc.relation.lastpage | 6603 | * |
dc.relation.journaltitle | Inorganic Chemistry | * |
dc.identifier.doi | 10.1021/acs.inorgchem.2c00430 | * |
dc.identifier.wosid | WOS:000798371200026 | * |
dc.identifier.scopusid | 2-s2.0-85129286873 | * |
dc.author.google | Zhang J. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | Seo M.S. | * |
dc.author.google | Fukuzumi S. | * |
dc.author.google | Nam W. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240426135715 | * |