CAREER: Nucleophilic, Radical, and Electrophilic Palladium Carbene Complexes: New Types of Reactivity For Palladium

职业：亲核、自由基和亲电钯卡宾配合物：钯的新型反应性

• 批准号: 1552397
• 负责人: Vlad Iluc
• 金额: $ 60.33万
• 依托单位: University of Notre Dame
• 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: 2016-05-01 至 2022-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1552397&HistoricalAwards=false
• 关键词: CAREER; Nucleophilic; Radical; Electrophilic; Palladium

In this CAREER project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Vlad M. Iluc of the Department of Chemistry at the University of Notre Dame is developing new tools for the selective reaction of hydrogen atoms bonded to common elements such as carbon, oxygen, boron, nitrogen and silicon. In this project, new approaches that involve metal-ligand cooperation are being developed to facilitate chemical transformations under mild conditions. This work is expected to have environmental and societal impact by providing basic knowledge that allows the development of catalytic processes involving water, alcohol, and amines, which are readily available chemical feedstocks. As the educational component of his project, Professor Iluc is developing an outreach program that focuses on mentoring of students from socio-economic groups that are underrepresented in science. The educational program provides educational opportunities for youth at the Bashor Children's Home and promotes their recruitment into science, technology, engineering and mathematics-based careers.The project targets (1) hydrogen transfer from the ligand to the metal and vice versa, which involves a nucleophilic carbene as part of a diphosphine pincer ligand; (2) hemilabile ligands, which incorporate olefins in a pincer architecture, in order to synthesize new untethered carbene nickel and palladium complexes; and (3) transfer of radical character from the supporting ligand to a coordinated substrate. The first class of complexes features nucleophilic carbene palladium complexes that are applied to the hydration, hydroalkoxylation, and hydroamination of olefins and other unsaturated substrates. The second class focuses on nickel and palladium and is applied to carbon (C)- silicon (Si) and C- boron (B) bond forming reactions. Finally, the third class features radical carbene palladium complexes that are applied to C-hydrogen (H) amination reactions with azides and olefin copolymerization reactions. Molecular models based on density functional theory guide these experiments. The educational project includes collaboration with the Bashor Children's Home, in Goshen, Indiana, a non-profit agency that provides help for at-risk children. In addition, the CAREER Award supports summer research activities at the University of Notre Dame. Visiting high school students work closely with graduate and undergraduate chemistry students in science activities related to research in the Iluc group.

在化学部化学催化计划资助的这项职业项目中，巴黎圣母院化学系的Vlad M. Iluc教授正在开发新的工具，以选择与碳，氧气，氧气，硼，氮气和硅的选择性反应的选择性反应。在这个项目中，正在开发涉及金属配体合作的新方法，以促进在轻度条件下的化学转化。预计这项工作将通过提供基本知识，从而开发涉及水，酒精和胺的基础知识，从而产生环境和社会影响，这些知识易于获得化学原料。作为他项目的教育部分，ILUC教授正在制定一项外展计划，该计划的重点是指导来自科学领域不足的社会经济团体的学生。该教育计划为Bashor儿童之家的青少年提供了教育机会，并将其招募到基于科学，技术，工程和数学的职业中。项目目标（1）从配体到金属的氢转移，而VICE VESA则涉及核友善的碳纤维，这是核友善的一部分。 （2）将烯烃掺入钳子结构中，以合成新的无束的卡宾镍和钯综合体； （3）从支撑配体转移到协调的底物。第一类配合物具有核碳酸钯络合物，可用于水合，羟基氧基化和盐水和其他不饱和底物的氢化化。第二类专注于镍和钯，并应用于碳（C） - 硅（Si）和C-硼（B）键形成反应。最后，第三类具有自由基碳钯络合物，这些复合物用于叠氮化物和烯烃共聚反应的C-氢化剂（H）胺化反应。基于密度功能理论的分子模型指导这些实验。该教育项目包括与Bashor儿童之家的合作，位于印第安纳州Goshen，这是一家非营利性机构，为处于危险的儿童提供帮助。此外，职业奖还支持巴黎圣母院的夏季研究活动。访问高中生与ILUC组研究有关的科学活动与研究生和本科化学学生紧密合作。