CAREER / SusChEM: Understanding and Utilization of the Secondary Coordination Sphere of Novel Biomimetic Catalysts for Small Molecule Activation

西华盛顿大学教授John D.Gilbertson在化学系化学催化(CAT)计划的支持下，开发具有生物灵感的、含有氧化还原活性的、非无辜的、吡啶二亚胺(PDI)金属络合物。配基。这些体系包括二次配位球体中的亲核/碱性底物导向器和/或氢键/质子导向器，以及配体支架中的基于配体的氧化还原活性中心。这些配体将被用来合成含有丰富的稀土金属的催化剂，并将被研究以发展关于将二氧化碳转化为可用原料和燃料(即CO、甲烷等)的分子水平的催化活性和选择性的广泛知识。对这些受生物启发的二氧化碳转化的研究将提供更好的理解，即如何调节金属酶模拟物的二级配位球以提供更好的结构/功能仿生。反过来，这些数据将被用于设计结构/功能模拟物，这些模拟物在有用的、生物启发的二氧化碳转化中发挥作用。除了二氧化碳减排的调查外，还将制定一个由本科生研究人员和WWU化学专业的学生组成的外展计划，旨在将化学引入当地媒体。二氧化碳是一种重要的环境污染物，需要合理的二氧化碳利用方法来缓解其作为温室气体的影响。二氧化碳生产一氧化碳(或甲烷)是利用二氧化碳作为原料的一条有吸引力的途径。二氧化碳是廉价和丰富的，重要的是，用于将其转化为可再生产品的催化剂(S)含有也廉价和丰富的金属(如铁、钴和锌)。

Professor John D. Gilbertson of Western Washington University is supported by the Chemical Catalysis (CAT) Program in the Division of Chemistry to develop bioinspired, pyridinediimine (PDI) metal complexes containing redox-active, ?non-innocent? ligands. These systems consist of nucleophilic/basic substrate directors and/or H-bond/proton-directors in the secondary coordination sphere, as well as ligand-based redox active sites in the ligand scaffold. These ligands will be used to synthesize catalysts containing earth abundant metals and will be studied in order to develop extensive knowledge concerning the molecular level catalytic activity and selectivity for the conversion of carbon dioxide into useable feedstocks and fuels (namely CO, methane, etc.). The investigation of these bioinspired conversions of carbon dioxide will provide a better understanding of how the secondary coordination sphere of metalloenzyme mimics can be regulated to provide better structural/functional biomimics. These data, in turn, will be utilized to design structural/functional mimics that are active in the useful, bioinspired transformations of carbon dioxide. In addition to the investigation of carbon dioxide reduction, an outreach program consisting of undergraduate researchers and WWU chemistry majors that aims to introduce chemistry into the local media will be developed. Carbon dioxide is a significant environmental contaminant and sensible methods of carbon dioxide utilization are needed for its mitigation as a greenhouse gas. The production of CO (or methane) from carbon dioxide is an attractive route to the utilization of carbon dioxide as a feedstock. Carbon dioxide is inexpensive and abundant, and it is important that catalysts utilized for its conversion(s) into renewable products contain metals that are also inexpensive and abundant (such as iron, cobalt, and zinc).