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

在这个由化学学部化学合成项目资助的项目中，卡尔顿学院的马修·t·怀特教授与一组本科生一起研究了以过渡金属/主基团键与酸性和碱性位点为特征的新型配合物的制备和反应性。在这些体系中，富含电子的过渡金属与缺乏电子的主基团协同作用，以促进困难的反应。这使得工业和环境重要分子（如二氧化碳和碳氢化合物）的新选择性转化得以发展。本项目是开发富土金属催化剂，将二氧化碳转化为化工原料。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。怀特教授还在卡尔顿学院开发基于课程的本科生研究体验（CUREs），并与一个推广项目合作，将当地高中生带入卡尔顿学院的化学实验室。该项目旨在理解和开发围绕金属后期/主基团相互作用的反应，使用具有约束金属-硅单键和多键的配合物作为原型。为了约束金属-硅键，硅基被拴在一个易于修饰的钳型配体中。富电子晚期金属和正电硅之间的差异导致的“电子挫折”，再加上两者之间键的动力学不稳定性，使得在催化碳氢化合物氧化和二氧化碳还原中应用强键激活的合作方法得以发展。金属/硅体系的光谱和反应性研究推动了这一研究的扩展，包括与硼基和羰基/羰基供体的钳形反应，以及与地球上丰富的金属的催化作用。该项目为本科生研究人员提供了一个培训基地，并支持与怀特博士在无机合成和x射线晶体学方面的兴趣相关的大学和高中教育的扩展。

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.