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.

在这个由化学系化学催化项目资助的项目中，伊利诺伊大学芝加哥分校的尼尔·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，新的催化剂设计采用了廉价、无害和富含地球元素的元素，以模仿基于昂贵、稀有和对环境有害的贵金属的传统催化剂的行为。本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。本项目中的催化剂设计将铁和铜等贱金属与直接的杂双金属金属-金属键配对。设计原则包括揭示杂双金属对的合作化学，这是任何一个单独的贱金属碎片都无法获得的，从而再现通常在单位点贵金属上观察到的化学，但以双金属的方式。使用模块化合成方法，很容易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射线晶体学、穆斯堡尔光谱和物理方法，与附近阿贡国家实验室的科学家合作，实现了对双金属核心的空间和电子环境的精确控制。这些杂双金属配合物在碳氢官能化催化和碳碳偶联催化中作为铱的替代品正在被探索。曼卡德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教授还共同创立并组织了芝加哥区域无机座谈会系列，以网络团体在芝加哥地区从事类似的项目。这项工作的更广泛的影响包括为未来的科学家提供一个培训环境，同时学习基本的科学原理，使贱金属能够在具有潜在社会重要性的催化反应中取代贵金属。