SusChEM: Base Metal Heterobimetallic Catalysts For C-H Borylation And C-C Coupling

在这个由化学部化学催化计划资助的项目中，伊利诺伊大学芝加哥分校的Neal Mankad教授专注于开发用更便宜，更容易获得的贱金属替代贵金属的战略。为了解决这个问题，新的催化剂设计具有廉价，良性和地球丰富的元素被用来模仿传统催化剂的行为，基于贵金属是昂贵的，稀有的，对环境有害的。该研究的最终目标是减少化学催化的环境和毒理学足迹，并转向更可持续的方法。该项目中的催化剂设计将铁和铜等贱金属与直接的异质金属-金属键结合。设计原理涉及揭示杂环对的合作化学，这是不可用的任何个别的贱金属片段，从而复制化学通常观察到在一个单一的网站贵金属，但在一个单一的方式。使用模块化的合成方法，几个候选催化剂很容易构建催化中的重要问题的探索。通过与附近的阿贡国家实验室的科学家合作进行的核磁共振光谱、红外光谱、X射线晶体学、穆斯堡尔光谱和物理方法，实现了对晶体核心的空间和电子环境的精确控制。这些杂环化合物正被探索作为C-H官能化催化中铱的替代物和C-C偶联催化中钯的替代物。Mankad教授正在将化学中的可持续性概念纳入芝加哥伊利诺伊大学的无机化学课程。此外，Mankad教授还共同创立和共同组织了芝加哥区域无机讨论会系列，以在芝加哥地区开展类似项目的网络团体。这项工作的更广泛影响包括为未来的科学家提供培训环境，同时学习基本科学原理，使贱金属在具有潜在社会重要性的催化反应中取代贵金属。

In this projected funded by the Chemical Catalysis program of the Chemistry Division, Professor Neal Mankad of the University of Illinois at Chicago focuses on the development of strategies for replacing noble metals with less expensive, and more easily available base metals. To approach this problem, new catalyst designs featuring inexpensive, benign, and earth-abundant elements are used to mimic the behavior of traditional catalysts based on precious metals that are expensive, rare, and environmentally hazardous. The ultimate goal of this research is to decrease the environmental and toxicological footprint of chemical catalysis and shift towards more sustainable methods.The catalyst design in this project pairs base metals such as iron and copper with direct, heterobimetallic metal-metal bonds. The design principle involves uncovering cooperative chemistry of the heterobimetallic pairs that is unavailable to either individual base metal fragment, thereby reproducing chemistry typically observed at a single-site noble metal, but in a bimetallic fashion. Using a modular synthetic approach, several candidate catalysts are readily constructed for probing important problems in catalysis. Precise control of the steric and electronic environments at the bimetallic cores is achieved, as characterized by NMR spectroscopy, IR spectroscopy, X-ray crystallography, Mossbauer spectroscopy, and physical methods performed in collaboration with scientists at nearby Argonne National Laboratory. These heterobimetallic complexes are being explored as replacements for iridium in C-H functionalization catalysis and for palladium in C-C coupling catalysis. The concepts of sustainability in chemistry are being incorporated by Professor Mankad into the inorganic chemistry curriculum at the University of Illinois at Chicago. In addition, Professor Mankad has co-founded and co-organized the Chicago Regional Inorganic Colloquium series to network groups working on similar projects in the Chicago area. The broader impacts of this work include providing a training environment for future scientists while learning the fundamental scientific principles that allow base metals to replace noble metals in catalytic reactions of potential societal importance.