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

在这个由化学系化学合成计划资助的项目中，Carleton学院的Matthew T.Whited教授与一组本科生合作，研究了具有过渡金属/主基键与酸性和碱性中心的新配合物的制备和反应活性。在这些体系中，富电子的过渡金属与贫电子的主基协同工作，以促进困难的反应。这使得二氧化碳和碳氢化合物等具有工业和环境重要性的分子能够开发出新的选择性转化。该项目正在开发富含地球的金属催化剂，将二氧化碳转化为化学原料。这是对实现可持续发展的重要贡献。因此，该项目有助于可持续化学、工程和材料(SusChEM)的努力。怀特教授还在卡尔顿学院发展以课程为基础的本科生研究经验(CURE)，并与一个外展计划合作，将当地高中生带到卡尔顿学院的化学实验室。这个项目寻求了解和发展围绕晚期金属/主基团相互作用的反应，使用具有受约束的金属-硅单键和多键的络合物作为原型。为了限制金属-硅键，硅基被连接到易于修饰的钳形配体中。富电子的晚期金属和正电性硅之间的差异造成的“电子受挫”，再加上每个金属的键的动力学不稳定性，使人们能够开发一种合作的方法来激活强键，并将其应用于催化碳氢化合物氧化和二氧化碳还原。对金属/硅体系的光谱和反应性研究推动了这项研究的扩大，包括具有硼基和碳基/卡宾给体的钳子，以及与富含稀土的金属的催化。该项目为本科生研究人员提供了一个培训场地，并支持扩大大学和高中的教育努力，这些努力与怀特博士对无机合成和X射线结晶学的兴趣有关。

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.