Investigations in the reactivity of hypervalent trifluoromethyl iodanes towards low-valent cobalt and nickel complexes - a contribution to the insight into metal-mediated electrophilic trifluoromethylations

高价三氟甲基碘与低价钴和镍配合物的反应性研究——有助于深入了解金属介导的亲电三氟甲基化

• 批准号: 320225637
• 负责人: Dr. Phil Liebing
• 金额: --
• 依托单位: Lehrstuhl für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/320225637?language=en
• 关键词: Investigations; reactivity; hypervalent; trifluoromethyl; iodanes

Hypervalent trifluoromethyl iodane(I) reagents ("Togni's reagents") are suitable for selective electrophilic trifluoromethylation of numerous substrates such as alcohols, thiols and various N and C nucleophiles. While the iodanes are activated for the mentioned reactions by lewis-acid (electrophilic) metal compounds, their behavior against nucleophilic metal compounds is rarely investigated so far. Within the scope of this project the reactivity of a carboxy iodane and a alkoxy iodane towards a series of simple low-valent CO and PPh3 complexes of cobalt and nickel is explored systematically. Thereby an oxidative trifluoromethylation of the metal atom is expected (e.g. M(0) to M(II)-CF3), implying a formal "umpolung" CF3+/CF3-. The focus of the research is how the properties and subsequent reactions of the products depend on metal, oxidation state, ligands and used iodane reagent. The so-gained findings can provide a basis for the development of new trifluoromethylation reactions and catalysts.

高价三氟甲基碘(I)试剂(Togni试剂)适用于醇、硫醇和各种N、C亲核试剂等多种底物的选择性三氟甲基化反应。虽然碘烷被路易斯酸(亲电)金属化合物激活用于上述反应，但它们对亲核金属化合物的行为迄今很少被研究。在本项目的范围内，系统地探索了羧基碘烷和烷氧基碘烷与一系列简单的低价CO和PPh_3钴镍络合物的反应性。因此，金属原子的氧化三氟甲基化(例如M(0)到M(II)-CF3)是预期的，意味着正式的“Upolung”CF3+/CF3-。研究的重点是产物的性质和后续反应如何依赖于金属、氧化态、配体和所用的碘烷试剂。所得结果可为开发新的三氟甲基化反应和催化剂提供依据。

项目成果

Perfluoroalkyl Cobaloximes: Preparation Using Hypervalent Iodine Reagents, Molecular Structures, Thermal and Photochemical Reactivity

全氟烷基钴肟：使用高价碘试剂制备、分子结构、热和光化学反应性

• DOI: 10.1021/acs.organomet.7b00892
• 发表时间: 2018
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: P. Liebing;F. Oehler;M. Wagner;P. F. Tripet;A. Togni
• 通讯作者: A. Togni