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

职业：SusChEM：具有金属/主族键的两亲钳型配合物的协同小分子活化

基本信息

批准号：
1552591
负责人：
Matthew Whited
金额：
$ 40万
依托单位：
Carleton College
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2016
资助国家：
美国
起止时间：
2016-06-01 至 2023-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1552591&HistoricalAwards=false
关键词：
CAREER SusChEM Cooperative Small Molecule

项目摘要

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.

在这个由化学系化学合成项目资助的项目中，卡尔顿学院的Matthew T. Whited教授与本科生研究小组合作，研究具有酸性和酸性的过渡金属/主族键的新型配合物的制备和反应性。基本站点。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。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。这是对实现可持续发展的重要贡献。因此，该项目为可持续化学、工程和材料 (SusChEM) 的努力做出了贡献。怀特教授还在卡尔顿学院开发基于课程的本科生研究经验（CURE），并与一个外展计划合作，将当地高中生带入卡尔顿学院化学实验室。该项目旨在了解和开发围绕后金属/主金属的反应-使用具有受限金属硅单键和多重键的配合物作为原型的基团相互作用。为了限制金属-硅键，将甲硅烷基束缚在易于修饰的钳型配体中。由于富含电子的晚期金属和正电性硅之间的差异而产生的“电子挫败”，再加上两者之间键的动力学不稳定性，使得开发出一种合作方法来实现强键活化，并应用于催化碳氢化合物氧化和二氧化碳减少。金属/硅系统的光谱和反应性研究推动了这项研究的扩展，包括硼基和碳基/卡宾供体的钳子以及地球上丰富的金属的催化。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 Whited 博士对无机合成和 X 射线晶体学兴趣相关的大学和高中教育工作。

项目成果

期刊论文数量（11）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Cobalt Silylenes as Platforms for Catalytic Nitrene‐Group Transfer by Metal–Ligand Cooperation.

钴硅烯作为金属-配体合作催化氮烯-基团转移的平台。

DOI：
10.1002/anie.202205748
发表时间：
2022
期刊：
Angewandte Chemie International Edition
影响因子：
0
作者：
Whited, Matthew T.;Han, Wenlai;Jin‐Lee, Helen J.;DiNardo, Zach;Watson, Emma;Zhang, Jia;Kohen, Daniela
通讯作者：
Kohen, Daniela

Computational and Experimental Investigation of Alkene Hydrogenation by a Pincer-Type [P 2 Si]Rh Complex: Alkane Release via Competitive σ-Bond Metathesis and Reductive Elimination

钳型 [P 2 Si]Rh 配合物对烯烃加氢的计算和实验研究：通过竞争性 Ï 键复分解和还原消除释放烷烃

DOI：
10.1021/acs.organomet.8b00922
发表时间：
2019
期刊：
Organometallics
影响因子：
2.8
作者：
Whited, Matthew T.;Trenerry, Michael J.;DeMeulenaere, Kaitlyn E.;Taylor, Buck L.
通讯作者：
Taylor, Buck L.

Pincer-supported metal/main-group bonds as platforms for cooperative transformations

夹钳支持的金属/主族债券作为合作转型的平台

DOI：
10.1039/d1dt02739e
发表时间：
2021
期刊：
Dalton Transactions
影响因子：
4
作者：
Whited, Matthew T.
通讯作者：
Whited, Matthew T.

trans -Acetyldicarbonyl(η 5 -cyclopentadienyl)[tris(3,5-dimethylphenyl)phosphane-κ P ]molybdenum(II)

反式-乙酰二羰基(δ 5 -环戊二烯基)[三(3,5-二甲基苯基)膦-δ P]钼(II)

DOI：
10.1107/s2414314617000426
发表时间：
2017
期刊：
IUCrData
影响因子：
0
作者：
Whited, Matthew T.;Ruffer, Eli J.;Zhang, Jia;Rabaey, Dominique J.;Janzen, Daron E.
通讯作者：
Janzen, Daron E.

Metal/Organosilicon Complexes: Structure, Reactivity, and Considerations for Catalysis

金属/有机硅配合物：结构、反应性和催化注意事项