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Developing homogeneous catalytic systems for aerobic oxidative methylation with methane

开发甲烷有氧氧化甲基化均相催化系统

基本信息

批准号：
1800089
负责人：
Andrei Vedernikov
金额：
$ 47万
依托单位：
University of Maryland, College Park
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：
2018-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800089&HistoricalAwards=false
关键词：
Developing homogeneous catalytic systems aerobic

项目摘要

With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Andrei Vedernikov of the University of Maryland College Park is developing novel platinum catalysts that convert methane from natural gas to high value-added chemicals. Oxygen from the air is used as a reactant and so these reactions avoid expensive and potentially toxic reagents Water is the major reaction by-product, so there is little waste produced. Methane is known for its chemical inertness and the development of greener processes for its economically-viable conversion to high-value added products is a fundamental chemical challenge. To tackle this problem, Dr. Vedernikov is studying novel platinum catalysts and designing new catalysts. He is taking advantage of theoretical and computational chemistry to explore plausible reaction pathways and guide his catalyst designs and experimental work. Dr. Vedernikov is working with high school students from low-income families. These students are interested in chemistry and have been selected by the local Washington D.C. section of the American Chemical Society (ACS Project SEED). The students intern in his lab, contributing to the experimental work in this project. Dr. Vedernikov is studying Shilov-type systems wherein electrophilic Pt(IV)Me intermediates are generated using O2 as the oxidant. Two complementary experimental approaches are used in this work. One relies on the use of redox mediators, e.g., Cu(II), while another utilizes a ligand-enabled O2 activation by Pt(II)R intermediates. The electrophilic Pt(IV)R intermediates are then intercepted by various nucleophiles (carboxylic acids, amines, etc.) to form hydrocarbon derivatives, such as quaternary ammonium salts or esters, that are protected from further oxidation. Dr Vedernikov is developing a fundamental mechanistic understanding of how the ligand environment at the Pt(II) center enables and tunes its reactivity toward both the hydrocarbon C-H bonds, and O2 to generate the Pt(IV)R intermediates. The viability of both approaches has been recently demonstrated in Dr. Vedernikov's group. Density functional theory is being used to guide the design of these novel systems and to carry out mechanistic analyses. The development of more efficient and environmentally benign protocols for methane functionalization is transformative. As a part of the broader impacts, Dr. Vedernikov is working with and training local high school, undergraduate and graduate students in this project.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.

在化学系化学催化项目的资助下，马里兰大学学院公园分校的 Andrei Vedernikov 博士正在开发新型铂催化剂，将甲烷从天然气转化为高附加值化学品。空气中的氧气被用作反应物，因此这些反应避免了昂贵且有潜在毒性的试剂。水是主要的反应副产品，因此几乎不产生废物。甲烷以其化学惰性而闻名，开发更环保的工艺以经济可行地将其转化为高附加值产品是一项基本的化学挑战。为了解决这个问题，Vedernikov 博士正在研究新型铂催化剂并设计新的催化剂。他利用理论和计算化学来探索合理的反应途径并指导他的催化剂设计和实验工作。维德尼科夫博士正在与低收入家庭的高中生一起工作。这些学生对化学感兴趣，并被美国化学会华盛顿特区当地分会（ACS Project SEED）选拔。学生们在他的实验室实习，为该项目的实验工作做出了贡献。 Vedernikov 博士正在研究 Shilov 型系统，其中使用 O2 作为氧化剂生成亲电子 Pt(IV)Me 中间体。这项工作使用了两种互补的实验方法。一种依赖于氧化还原介体的使用，例如 Cu(II)，而另一种则利用 Pt(II)R 中间体的配体启用的 O2 活化。然后，亲电 Pt(IV)R 中间体被各种亲核试剂（羧酸、胺等）拦截，形成烃衍生物，例如季铵盐或酯，并防止进一步氧化。 Vedernikov 博士正在对 Pt(II) 中心的配体环境如何启用和调整其对碳氢化合物 C-H 键和 O2 的反应性以生成 Pt(IV)R 中间体有一个基本的机制理解。 Vedernikov 博士的团队最近证明了这两种方法的可行性。密度泛函理论被用来指导这些新颖系统的设计并进行机械分析。开发更高效、更环保的甲烷功能化方案具有变革性意义。作为更广泛影响的一部分，Vedernikov 博士正在该项目中与当地高中、本科生和研究生合作并对其进行培训。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛影响审查标准进行评估，被认为值得支持。

项目成果

期刊论文数量（8）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

CH 3 –X Reductive Elimination Reactivity of Pt IV Me Complexes Supported by a Sulfonated CNN Pincer Ligand (X = OH, CF 3 CO 2 , PhNMe 2 + )

磺化 CNN Pincer 配体支持的 Pt IV Me 配合物的 CH 3 →X 还原消除反应性 (X = OH, CF 3 CO 2 , PhNMe 2 )

DOI：
10.1021/acs.organomet.9b00702
发表时间：
2019
期刊：
Organometallics
影响因子：
2.8
作者：
Ruan, Jiaheng;Wang, Daoyong;Vedernikov, Andrei N.
通讯作者：
Vedernikov, Andrei N.

Consecutive C–H and O 2 Activation at a Pt(II) Center To Produce Pt(IV) Aryls

Pt(II) 中心连续 C–H 和 O 2 活化生成 Pt(IV) 芳基

DOI：
10.1021/acs.organomet.8b00662
发表时间：
2018
期刊：
Organometallics
影响因子：
2.8
作者：
Watts, David;Zavalij, Peter Y.;Vedernikov, Andrei N.
通讯作者：
Vedernikov, Andrei N.

Catalytic Deuteration of C(sp 2 )–H Bonds of Substituted (Hetero)arenes in a Pt(II) CNN-Pincer Complex/2,2,2-Trifluoroethanol- d 1 System: Effect of Substituents on the Reaction Rate and Selectivity

Pt(II) CNN-Pincer 配合物/2,2,2-三氟乙醇- d 1 体系中取代（杂）芳烃 C(sp 2 )–H 键的催化氘化：取代基对反应速率和

DOI：
10.1021/acs.organomet.0c00652
发表时间：
2020
期刊：
Organometallics
影响因子：
2.8
作者：
Kramer, Morgan;Watts, David;Vedernikov, Andrei N.
通讯作者：
Vedernikov, Andrei N.

Oxidation of Methylplatinum(II) Complexes K[(L)Pt II Me] with O 2 and C(sp 3 )-X (X = O and C) Reductive Elimination Reactivity of Methylplatinum(IV) Products ( L )Pt IV Me(OH): The Effect of Structure of Sulfonated CNN-Pincer Ligands L

甲基铂(II) 络合物 K[(L)Pt II Me] 与 O 2 和 C(sp 3 )-X (X = O 和 C) 的氧化甲基铂(IV) 产物的还原消除反应性 ( L )Pt IV Me(

DOI：
10.1021/acs.organomet.2c00371
发表时间：
2022
期刊：
Organometallics
影响因子：
2.8
作者：
Ruan, Jiaheng;Wang, Daoyong;Kramer, Morgan J.;Zavalij, Peter Y.;Vedernikov, Andrei N.
通讯作者：
Vedernikov, Andrei N.

An Electron-Poor Dioxa-[2.1.1]-(2,6)-pyridinophane Ligand and Its Application in Cu-Catalyzed Olefin Aziridination

一种贫电子二氧杂-[2.1.1]-(2,6)-吡啶芬配体及其在铜催化烯烃氮丙啶化反应中的应用