CAREER: SusChEM: Cooperative Small-Molecule Activation by Ambiphilic Pincer-Type Complexes Featuring Metal/Main-Group Bonds

本研究由化学系化学合成项目资助，Matthew T.卡尔顿学院的怀特与一个本科生研究小组合作，研究具有过渡金属/主基团键与酸性和碱性位点的新络合物的制备和反应性。在这些系统中，富电子过渡金属与贫电子主基团协同作用，以促进困难的反应。这允许开发工业和环境重要分子如二氧化碳和烃的新的选择性转化。该项目正在开发地球上丰富的金属催化剂，将二氧化碳转化为化学原料。这是对实现可持续性的重要贡献。因此，该项目有助于可持续化学，工程和材料（SusChEM）的努力。Whited教授还在卡尔顿学院开发基于课程的本科生研究体验（CURE），并与一个外展计划合作，将当地高中生带入卡尔顿学院的化学实验室。该项目旨在利用具有受限金属-硅单键和多键的复合物作为原型，了解和开发围绕后期金属/主基团相互作用的反应。为了限制金属-硅键，甲硅烷基被束缚到容易修饰的钳型配体中。“电子挫折”之间的差距所产生的富电子后期金属和正电性硅，结合键的动力学不稳定性，每个，允许开发一种合作的方法，以强键活化与应用在催化烃氧化和二氧化碳还原。金属/硅系统的光谱和反应性研究促使这项研究的扩展，包括钳与硼基和碳基/卡宾捐助者，以及与地球丰富的金属催化。该项目为本科研究人员提供了一个培训基地，并支持扩大与怀特博士在无机合成和X射线晶体学方面的兴趣有关的大学和高中教育工作。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Matthew T. Whited of Carleton College works with a research group of undergraduate students to investigate the preparation and reactivity of new complexes featuring transition metal/main-group bonds with acidic and basic sites. In these systems an electron-rich transition metal works synergistically with an electron-poor main-group to facilitate difficult reactions. This allows the development of new selective transformations of industrially and environmentally important molecules such as carbon dioxide and hydrocarbons. This project is developing earth abundant metal catalysts to convert carbon dioxide into chemical feedstocks. This is important contribution to achieving sustainability. As such the project contributes to the Sustainable Chemistry, Engineering, and Materials (SusChEM) effort. Professor Whited is also developing course-based undergraduate research experiences (CUREs) at Carleton College and working with an outreach program to bring local high-school students into Carleton College chemistry laboratories.This project seeks to understand and develop reactions around late-metal/main-group interactions using complexes featuring constrained metal-silicon single and multiple bonds as prototypes. In order to constrain the metal-silicon linkage, the silyl group is tethered into an easily modified pincer-type ligand. The "electronic frustration" resulting from the disparity between electron-rich late metals and electropositive silicon, combined with the kinetic lability of bonds to each, allows the development of a cooperative approach to strong-bond activation with applications in catalytic hydrocarbon oxidation and carbon dioxide reduction. Spectroscopic and reactivity studies of metal/silicon systems motivate the expansion of this research to include pincers with boryl and carbyl/carbene donors as well as to catalysis with earth-abundant metals. The project provides a training ground for undergraduate researchers and supports the expansion of both college- and high-school education efforts related to Dr. Whited's interests in inorganic synthesis and X-ray crystallography.