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Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

机译:沮丧的路易斯对催化中二氧化碳和杂环官能化的设计原理

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This account describes our work on the use of ambiphilic molecules as catalysts for the reduction of carbon dioxide. Starting with the discovery that aluminum ambiphilic species (Me2PCH2AlMe2)2 (1) and AI (C6H4-PPh2)(3) (5) could coordinate CO2 but showed significant instability, we found that phosphinoborane Ph2P-2-Bcat-C6H4 (7) was an exceptional catalyst for the hydroboration-of CO2 to methoxyboranes, molecules that can be readily hydrolyzed to methanol. A mechanistic investigation allowed us to outline the similarities between the catalytic activity of frustrated Lewis pairs (FLPs) and that of transition metal complexes. We were able to extrapolate four important guidelines, described in this account, for the conception of efficient metal-free catalysts. We demonstrate that using these concepts, it was possible to rationally design FLP catalysts for the C-H borylation of heteroarenes. (C) 2016 Elsevier B.V. All rights reserved.
机译:该说明描述了我们在使用歧义性分子作为减少二氧化碳的催化剂方面的工作。从发现铝两性物种(Me2PCH2AlMe2)2(1)和AI(C6H4-PPh2)(3)(5)的发现开始,我们发现膦硼烷Ph2P-2-Bcat-C6H4(7)是将CO2加氢硼化为甲氧基硼烷(一种可轻松水解为甲醇的分子)的出色催化剂。机械研究使我们能够概述沮丧的路易斯对(FLP)与过渡金属络合物的催化活性之间的相似性。我们能够推断出此帐户中描述的四个重要指导原则,以说明有效的无金属催化剂的概念。我们证明,使用这些概念,可以合理地设计用于杂芳烃C-H硼化的FLP催化剂。 (C)2016 Elsevier B.V.保留所有权利。

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