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金属-配位子協働作用とフルオロアルキル基導入反応に向けた非ホスフィン配位子を有する遷移金属錯体の合成と反応
https://doi.org/10.15102/0002000683
https://doi.org/10.15102/0002000683080fee38-c9f5-46aa-a2bd-b8682934d1c9
| 名前 / ファイル | ライセンス | アクション |
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DinhHoanFulltext.pdf (5.4 MB)
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DinhHoanExamAbstract.pdf (48 KB)
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| Item type | 学位論文 / Thesis or Dissertation(1) | |||||||
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| 公開日 | 2024-11-13 | |||||||
| タイトル | ||||||||
| タイトル | 金属-配位子協働作用とフルオロアルキル基導入反応に向けた非ホスフィン配位子を有する遷移金属錯体の合成と反応 | |||||||
| 言語 | ja | |||||||
| タイトル | ||||||||
| タイトル | Synthesis and Reactivity of Transition Metal Complexes Supported by Non-Phosphine Ligands in Metal-Ligand Cooperation and Fluoroalkyl Incorporation | |||||||
| 言語 | en | |||||||
| 言語 | ||||||||
| 言語 | eng | |||||||
| 資源タイプ | ||||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_db06 | |||||||
| 資源タイプ | doctoral thesis | |||||||
| ID登録 | ||||||||
| ID登録 | 10.15102/0002000683 | |||||||
| ID登録タイプ | JaLC | |||||||
| アクセス権 | ||||||||
| アクセス権 | open access | |||||||
| アクセス権URI | http://purl.org/coar/access_right/c_abf2 | |||||||
| 著者 (英) |
Dinh, Hoan
× Dinh, Hoan
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| 抄録 | ||||||||
| 内容記述タイプ | Abstract | |||||||
| 内容記述 | The thesis describes the synthesis and reactivity of metal complexes supported by nonphosphine ligands in metal-ligand cooperation and fluoroalkyl incorporation. The first chapter introduces the literature review on metal-ligand cooperation as a tool for bond activation and catalysis, and the synthesis of manganese(I) and ruthenium(II) complexes supported by non-phosphine N,S-donor macrocyclic pyridinophane ligands. These complexes undergo a facile, reversible single and double dearomatization in pyridine rings in the presence of the base. In the second chapter, we continue utilizing the macrocyclic pyridinophane scaffolds for the synthesis of high-valent manganese(III) complexes via oxidative addition of aryl bromide to manganese(I) precursor and study Ar-Br reductive elimination via one-electron oxidation. We also present the new synthetic route to cyclometalated high-valent manganese(III) fluoro complexes using a trifluoromethylating reagent via transmetalation followed by α-fluorine elimination, resulting in the release of a difluorocarbene. That facile generation of a difluorocarbene could be utilized in difluorocarbenation of alkenes and alkynes using Zn trifluoromethyl reagent at lower temperatures and shorter time as compared to a manganese-free reaction. The third chapter includes literature review on radical fluoroalkylation mediated by first-row transition metal complex, then focusing on the synthesis of cobalt perfluoroethyl complexes supported by simple N-donor naphthyridine ligands. These complexes showed Co-C2F5 bond homolysis under visible-light irradiation and could be utilized as catalysts for light-induced C-H bond perfluoroalkylation in arenes using Togni reagent. | |||||||
| 口頭試問日 | ||||||||
| 値 | 2024-05-14 | |||||||
| 学位授与年月日 | ||||||||
| 学位授与年月日 | 2024-06-30 | |||||||
| 学位名 | ||||||||
| 言語 | en | |||||||
| 学位名 | Doctor of Philosophy | |||||||
| 学位授与番号 | ||||||||
| 学位授与番号 | 甲第154号 | |||||||
| 学位授与機関 | ||||||||
| 学位授与機関識別子Scheme | kakenhi | |||||||
| 学位授与機関識別子 | 38005 | |||||||
| 言語 | en | |||||||
| 学位授与機関名 | Okinawa Institute of Science and Technology Graduate University | |||||||
| 著者版フラグ | ||||||||
| 出版タイプ | VoR | |||||||
| 出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||||
| 権利 | ||||||||
| 言語 | en | |||||||
| 権利情報 | © 2024 The Author. | |||||||
| 開始ページ | 1 | |||||||
