Heterolytic dihydrogen activation by "antagonistic" Lewis pairs

“拮抗”路易斯对的杂解二氢活化

• 批准号: 153069397
• 负责人: Professor Dr. Gerhard Erker
• 金额: --
• 依托单位: Organisch-Chemisches Institut
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2009
• 资助国家: 德国
• 起止时间: 2008-12-31 至 2014-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/153069397?language=en
• 关键词: Heterolytic; dihydrogen; activation; antagonistic; Lewis

Hydroboration of a series of enamines with Piers’ borane gave new intramolecular vicinal N/B frustrated Lewis pairs (FLPs). These examples feature weak intramolecular nitrogenboron interactions. The activation barrier for ring opening to the active FLPs was determined for chiral examples by dynamic 19F NMR spectroscopy. Similar P/B FLPs were prepared and the activation barrier of the cleavage of their weak P−B bonds determined as well. Many of these new systems cleave dihydrogen heterolytically under mild conditions. Some serve as metal-free catalysts for the hydrogenation of electron-rich unsaturated substrates (enamines, dienamines, imines, etc.). We have also developed a protocol for FLP catalyzed hydrogenation of electron-poor olefins and alkynes (bulky ynones and enones). This has considerably extended the application potential of these new metal-free main-group element dihydrogen activators.

一系列烯胺与Piers‘s硼烷的氢化反应得到了新的分子内邻位N/B受阻Lewis对(FLPs)。这些例子的特点是分子内氮硼相互作用很弱。用动态~(19)F核磁共振波谱测定了手性实例的活性FLP的开环活化势垒。制备了类似的P/B FLP，并测定了它们的弱P-−-B键断裂的活化势垒。这些新体系中的许多在温和的条件下以异相分解的方式分解二氢。一些用作富含电子的不饱和底物(烯胺、二烯胺、亚胺等)加氢的无金属催化剂。我们还开发了一种FLP催化的贫电子烯烃和炔烃(大体积的炔酮和烯酮)加氢反应的方案。这大大扩展了这些新型无金属主族元素二氢活化剂的应用潜力。