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

在这项由化学系化学催化计划资助的计划中，芝加哥伊利诺伊大学的尼尔·曼卡德教授专注于开发用更便宜、更容易获得的贱金属取代贵金属的策略。为了解决这个问题，以廉价、无害和富含稀土元素为特征的新型催化剂设计被用来模仿基于贵金属的传统催化剂的行为，贵金属是昂贵的、稀有的和对环境有害的。这项研究的最终目标是减少化学催化的环境和毒物足迹，并转向更可持续的方法。该项目的催化剂设计将贱金属(如铁和铜)与直接的双金属金属-金属键配对。设计原则涉及揭示异双金属对的合作化学，这是任何一个贱金属片段都不能获得的，从而重现通常在单位贵金属观察到的化学，但以双金属的方式。利用模块化的合成方法，可以很容易地构建几个候选催化剂来探索催化中的重要问题。通过核磁共振光谱、红外光谱、X射线结晶学、穆斯堡尔光谱和与附近阿贡国家实验室的科学家合作执行的物理方法，实现了对双金属核心的空间和电子环境的精确控制。这些异双金属配合物正被探索在C-H功能化催化中作为Ir的替代物，在C-C偶联催化中作为Pd的替代物。曼卡德教授正在将化学可持续发展的概念纳入伊利诺伊大学芝加哥分校的无机化学课程。此外，曼卡德教授还共同创立并共同组织了芝加哥地区无机学术讨论会系列，为芝加哥地区从事类似项目的团体建立网络。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，同时学习使贱金属在具有潜在社会意义的催化反应中取代贵金属的基本科学原理。

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.