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

• 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

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.

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。富电子晚期金属和正电性硅之间的差异导致的“电子挫败”，加上彼此键的动力学不稳定性，使得可以开发一种强键活化的合作方法，并应用于催化碳氢化合物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。

项目成果

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
• 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

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.

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.

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
• 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

• DOI: 10.1080/02603594.2020.1737026
• 发表时间: 2020
• 期刊: Comments on Inorganic Chemistry
• 影响因子: 5.4
• 作者: Whited, Matthew T.;Taylor, Buck L.
• 通讯作者: Taylor, Buck L.