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

这一奖项授予马里兰大学学院公园分校的Andrei Vedernikov教授，目的是研究一些新的有机铂(II)和有机钯(II)化合物在水介质中与氧和过氧化氢激活炔烃和芳亚胺的反应性。本研究的重点是金属有机氧化和C-X还原消除的结构-反应活性关系，这对发展选择性铂和钯催化反应具有重要意义。一些单烃基铂(IV)和单烃基钯(IV)配合物在水介质中对C-X键还原消除的反应活性将被详细表征，包括动力学研究和密度泛函模拟。将开发一种新型的螯合半活性配体，用于催化选择氧化水介质中的烯烃和炔烃。最近发现的一种催化反应，包括钯催化芳亚胺与过氧化氢的CH-羟基化，将受到详细的机理分析，并扩大其底物范围。还将探索新的催化工艺的可行性，如以O2为氧化剂的氧化CH氟化和乙烷和苯的氧化偶联。了解以氧和过氧化氢为氧化剂，水为溶剂，有机钯(II)和有机铂(II)络合物为底物的反应的结构-反应性关系，将对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对研究生、本科生和高中生进行专业培训。来自ACS SEED项目和当地高中的暑期研究学生将参与其中。来自马里兰州和马里兰大学代表性不足群体的本科生和研究生将参加。

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.