Novel M-C Bond Functionalization Reactions in Aqueous and Hydrocarbon Media Involving M(II)/M(IV) Redox Couples (M = Pd, Pt)

涉及 M(II)/M(IV) 氧化还原对（M = Pd、Pt）的水和碳氢化合物介质中的新型 M-C 键功能化反应

• 批准号: 1112019
• 负责人: Andrei Vedernikov
• 金额: $ 45.6万
• 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: 2011
• 资助国家: 美国
• 起止时间: 2011-08-01 至 2015-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1112019&HistoricalAwards=false
• 关键词: Novel; Bond; Functionalization; Reactions; Aqueous

This award to Professor Andrei Vedernikov at the University of Maryland at College Park is to study the reactivity of a number of new organoplatinum(II) and organopalladium(II) compounds that activate alkynes and arylimines with oxygen and hydrogen peroxide in aqueous media. This study focuses on the structure-reactivity relationships for organometallic oxidation and C-X reductive elimination, which are of fundamental importance for developing selective platinum- and palladium-mediated catalytic reactions. The reactivity of some monohydrocarbyl platinum(IV) and monohydrocarbyl palladium(IV) complexes with respect to C-X bond reductive elimination will be characterized in detail in aqueous media, including kinetics studies and DFT modeling. New chelating semilabile ligands will be developed for the catalytic selective aerobic oxidation of olefins and alkynes in aqueous media. A recently discovered catalytic reaction involving Pd- catalyzed CH- hydroxylation of arylimines with hydrogen peroxide, will be subjected to a detailed mechanistic analysis and its substrate scope expanded. The feasibility of new catalytic processes, such as oxidative CH fluorination with O2 as the oxidant and oxidative coupling of ethane and benzene, will also be explored. Knowledge of structure-reactivity relationships for reactions involving oxygen and hydrogen peroxide as oxidants, water as solvent and organopalladium(II) and organoplatinum(II) complexes as substrates will be valuable for the development of new selective and efficient "green" synthetic protocols. An important outcome of this research is the professional training of graduate, undergraduate and high school students. Summer research students from the ACS SEED program and local high schools will be involved. Undergraduate and graduate students from underrepresented groups in Maryland and at the University of Maryland will participate.

该奖项授予马里兰州大学帕克分校的Andrei Vedernikov教授，旨在研究一些新的有机铂（II）和有机钯（II）化合物的反应性，这些化合物可在水介质中用氧气和过氧化氢活化炔和芳基亚胺。 本研究的重点是有机金属氧化和C-X还原消除，这是发展选择性铂和钯介导的催化反应的根本重要性的结构-反应性关系。 一些单烃基铂（IV）和单烃基钯（IV）配合物相对于C-X键还原消除的反应性将在水介质中详细表征，包括动力学研究和DFT建模。新型螯合半不稳定配体将被开发用于水介质中烯烃和炔烃的催化选择性有氧氧化。 本文对新近发现的钯催化的芳基亚胺与过氧化氢的CH-羟基化反应进行了详细的机理分析，并扩展了反应的底物范围。 探索新的催化工艺的可行性，如以O2为氧化剂的氧化甲烷化和乙烷与苯的氧化偶联。 以氧和过氧化氢为氧化剂，水为溶剂，有机钯（II）和有机铂（II）配合物为底物的反应的结构-反应性关系的研究对于开发新的选择性和高效的“绿色”合成方案具有重要意义。 这项研究的一个重要成果是研究生、本科生和高中生的专业培训。 来自ACS SEED项目和当地高中的暑期研究生将参与其中。 来自马里兰州和马里兰州大学代表性不足群体的本科生和研究生将参加。