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

SusChEM：用于 C-H 硼化和 C-C 偶联的贱金属异双金属催化剂

• 批准号: 1362294
• 负责人: Neal Mankad
• 金额: $ 37.5万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-05-15 至 2017-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362294&HistoricalAwards=false
• 关键词: SusChEM; Base; Metal; Heterobimetallic; Catalysts

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.

在化学部化学催化计划资助的预计中，芝加哥伊利诺伊大学的尼尔·曼卡德（Neal Mankad）教授着重于制定以更便宜和更容易获得的基准金属代替贵族金属的策略。为了解决这个问题，使用廉价，良性和地球元素的新催化剂设计用于模仿基于贵金属基于贵金属的传统催化剂的行为，这些金属昂贵，稀有且环境危险。这项研究的最终目的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。该项目的催化剂设计对基本金属（例如铁和铜）与直接的，杂质的金属金属键。该设计原理涉及揭示异金属对的合作化学，这是单个碱金属碎片不可用的，从而再现了通常在单个位置贵金属中观察到的化学反应，但以双金属方式观察到。使用模块化合成方法，很容易构建几种候选催化剂，以探测催化中的重要问题。以NMR光谱，IR光谱，X射线晶体学，Mossbauer光谱法以及与附近的Argonne国家实验室的科学家合作执行的，可以实现双金属岩心的空间和电子环境的精确控制。这些杂物复合物被探索为替代C-H功能化催化中的虹膜和C-C偶联催化中的钯。曼卡德教授将化学可持续性的概念纳入了芝加哥伊利诺伊大学的无机化学课程。此外，曼卡德（Mankad）教授还共同创立并组织了芝加哥地区无机座谈会系列，以在芝加哥地区类似项目的网络组中进行。这项工作的更广泛的影响包括为未来的科学家提供培训环境，同时学习基本的科学原理，这些科学原则使碱金属能够在潜在社会重要性的催化反应中代替贵金属。