Activation of Carbon-Hydrogen Bonds at Multinuclear Metal Sites

多核金属位点碳氢键的活化

• 批准号: 1764192
• 负责人: Richard Adams
• 金额: $ 44.84万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-06-15 至 2023-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764192&HistoricalAwards=false
• 关键词: Activation; Carbon; Hydrogen; Bonds; Multinuclear

Simple hydrocarbons such as methane and ethane are now available from abundant supplies of natural gas. However, since these materials cannot easily be converted into other products, they are not good feedstocks for the chemical industry. In large part, this difficulty arises because the carbon-hydrogen (C-H) bonds in hydrocarbons are relatively unreactive. In this project, funded by the Chemical Synthesis Program of the Chemistry Division, Professor Richard D. Adams, Department of Chemistry and Biochemistry at the University of South Carolina, is developing methods to activate hydrocarbon C-H bonds. Metal complexes having two or more metal atoms are designed so that several C-H bonds in a hydrocarbon interact with the metals. These interactions activate the bonds and allow the hydrocarbons to be converted into valuable products, such as alcohols, aldehydes and carboxylic acids. These lead to new processes for the production of industrial materials. In addition to the scientific component, the project involves both graduate and undergraduate students, including ones from underrepresented groups and prepares them for careers in science and technology.Multinuclear complexes of precious metal elements, such as ruthenium, rhodium, rhenium, iridium, and platinum, are evaluated for their ability to activate hydrocarbon C-H bonds. By using metal complexes having two or more metal atoms, multiple CH activations are achieved and several functionalities are introduced on a single hydrocarbon. The studies target C-C and C-O bond forming processes and include mechanistic investigations to uncover details of the transformations. New bimetallic complexes are converted into bimetallic nanoparticles to create a new generation of high activity heterogeneous catalysts. Broader impacts include the development of new processes for the conversion of simple hydrocarbons and related resources into valuable chemicals for use as industrial feedstocks. Graduate and undergraduate students are trained in the latest methods of scientific inquiry and analysis.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

简单的碳氢化合物，如甲烷和乙烷，现在可以从丰富的天然气供应中获得。然而，由于这些材料不易转化为其他产品，因此它们不是化学工业的良好原料。在很大程度上，出现这种困难是因为碳氢化合物中的碳氢键相对不活泼。南卡罗来纳大学化学与生物化学系的Richard D. Adams教授在化学合成项目资助下，正在开发激活碳氢化合物C-H键的方法。具有两个或多个金属原子的金属配合物被设计成碳氢化合物中的几个碳氢键与金属相互作用。这些相互作用激活了化学键，使碳氢化合物转化为有价值的产物，如醇、醛和羧酸。这导致了工业材料生产的新工艺。除了科学部分外，该项目还涉及研究生和本科生，包括来自代表性不足群体的学生，并为他们从事科学和技术职业做好准备。贵重金属元素的多核配合物，如钌、铑、铼、铱和铂，被评价为它们激活碳氢化合物C-H键的能力。通过使用具有两个或多个金属原子的金属配合物，可以在单个碳氢化合物上实现多个CH活化并引入多个官能团。研究的目标是C-C和C-O键形成过程，并包括揭示转化细节的机制研究。新的双金属配合物转化为双金属纳米颗粒，创造了新一代高活性的非均相催化剂。更广泛的影响包括发展将简单碳氢化合物和有关资源转化为用作工业原料的有价值化学品的新工艺。研究生和本科生接受最新的科学探究和分析方法的培训。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

The coordination and activation of azobenzene by Ru5(μ5-C) cluster complexes

Ru5(μ5-C)簇配合物对偶氮苯的配位与活化

• DOI: 10.1016/j.jorganchem.2018.10.004
• 发表时间: 2018
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Adams, Richard D.;Akter, Humaiara;Smith, Mark D.;Tedder, Jonathan D.
• 通讯作者: Tedder, Jonathan D.

C – C Coupling of Alkynes to the CH2 Group in a 1-Phosphonioethenyl Ligand in a Zwitterionic Dirhenium Carbonyl Complex

• DOI: 10.1016/j.jorganchem.2022.122490
• 发表时间: 2022-08
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: R. D. Adams;Meenal Kaushal;P. Pellechia;Mark D Smith

Multiple C−H Bond Activations in Corannulene by a Dirhenium Complex

二铼络合物对 Corannulene 中的多个 C–H 键激活

• DOI: 10.1002/chem.201806405
• 发表时间: 2019
• 期刊: Chemistry – A European Journal
• 作者: Adams, Richard D.;Dhull, Poonam;Pennachio, Matthew;Petrukhina, Marina A.;Smith, Mark D.
• 通讯作者: Smith, Mark D.

Reductive coupling of diisopropylcarbodiimide by a dirhenium carbonyl complex

• DOI: 10.1016/j.jorganchem.2019.06.027
• 发表时间: 2019-10
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: R. D. Adams;Poonam Dhull;Joseph M Parr;J. Tedder

Alkyne Coupling and Cyclization on Metal Cluster Complexes. Additions and Couplings of Dimethyl acetylenedicarboxylate to Ru6(μ6-C)(CO)14(μ3-η4-C4H4)

金属簇配合物的炔偶联和环化。

• DOI: 10.1016/j.jorganchem.2022.122538
• 发表时间: 2022
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Adams, Richard D.;Kaushal, Meenal;Smith, Mark D.;Wakdikar, Nutan D.
• 通讯作者: Wakdikar, Nutan D.