SusChEM: IUPAC: Harnessing the Unquenched Reactivity of Novel Frustrated Lewis Pairs for Transition Metal-Free Hydrogenation Catalysis

在这个由化学系化学催化计划资助的项目中，德克萨斯理工大学的Clemens Krempner教授研究了使用受挫的刘易斯对（FLP）作为昂贵的替代品，不太丰富，有毒的贵金属用于催化氢化不饱和有机物种。 FLP是空间位阻的刘易斯酸-碱对，由于它们不能形成经典的路易斯酸-碱复合物，因此具有未淬灭的反应性。新型组合的刘易斯酸和碱，能够可逆地裂解二氢，确定由一个组合的计算/实验方法。 有吸引力的弱刘易斯酸包括硼酸和硼酸酯，因为这些化合物容易由廉价的起始材料合成或以低成本商购获得。磷腈和胍用作基础组分。催化剂开发的进展通过模块化FLP合成、详细的催化测试和对新型催化剂和潜在催化机制的计算研究的组合而放大。该项目是与李淑华教授（南京大学，中国南京）和Juergen Klankermayer教授（亚琛工业大学，亚琛，德国）合作进行的。这三个集团联合收割机将各自的专业领域结合在一起，生产不含过渡金属的亚胺、酮和烯烃加氢产品，这些产品是制药行业的重要底物。 这项工作的更广泛影响包括对博士后研究员、研究生和本科生的领导能力培训，以及思想和专门知识的国际交流。

In this project, funded by the Chemical Catalysis Program of the Chemistry Division, Professor Clemens Krempner of Texas Tech University examines the use of frustrated Lewis pairs (FLPs) as replacements for expensive, less abundant, and toxic precious metals used in the catalytic hydrogenation of unsaturated organic species. FLPs are sterically-encumbered Lewis acid-base pairs of unquenched reactivity due to their inability to form classical Lewis-acid-base complexes. Novel combinations of Lewis acids and bases, capable of reversibly cleaving dihydrogen, are identified by a combined computational / experimental approach. Attractive weak Lewis acids include boronic and boric esters, as these compounds are readily synthesized from inexpensive starting materials or are commercially available at low cost. Phosphazenes and guanidines are used as the base components. Progress in catalyst development is amplified by the combination of modular FLP synthesis, detailed catalytic testing, and computational investigations on novel catalysts and the underlying catalytic mechanisms. This project is performed in collaboration with Professor Shuhua Li (Nanjing University, Nanjing, China) and Professor Juergen Klankermayer (RWTH Aachen, Aachen, Germany). Together, these three groups combine their separate areas of expertise to produce transition metal-free hydrogenation of imines, ketones and olefins - important substrates in the pharmaceutical industry. The broader impacts of this work include leadership training for postdoctoral fellows and graduate and undergraduate students and an international exchange of ideas and expertise.