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.

在这个由化学系化学催化项目资助的CAREER项目中，Vlad M。圣母大学化学系的Iluc正在开发新的工具，用于与碳、氧、硼、氮和硅等常见元素键合的氢原子的选择性反应。在该项目中，正在开发涉及金属配体合作的新方法，以促进温和条件下的化学转化。这项工作预计将产生环境和社会影响，提供基础知识，允许涉及水，酒精和胺，这是现成的化学原料的催化过程的发展。作为他的项目的教育组成部分，Iluc教授正在开发一个外展计划，重点是指导那些在科学领域代表性不足的社会经济群体的学生。该教育方案为Bashor儿童之家的青少年提供教育机会，并促进他们进入科学、技术、工程和制药行业，该项目的目标是（1）氢从配体转移到金属，反之亦然，这涉及亲核卡宾作为双膦钳形配体的一部分;（2）半不稳定配体，其在钳形结构中引入烯烃，以合成新的未束缚的卡宾镍和钯络合物;和（3）自由基特征从支持配体转移到配位底物。第一类络合物的特征在于亲核卡宾钯络合物，其应用于烯烃和其它不饱和底物的水合、氢烷氧基化和氢胺化。第二类集中于镍和钯，并应用于碳（C）-硅（Si）和C-硼（B）键形成反应。最后，第三类特征在于自由基卡宾钯络合物，其应用于与叠氮化物的C-氢（H）胺化反应和烯烃共聚反应。基于密度泛函理论的分子模型指导这些实验。该教育项目包括与印第安纳州歌珊的Bashor儿童之家合作，这是一个为处境危险的儿童提供帮助的非营利机构。此外，CAREER奖还支持圣母大学的夏季研究活动。访问高中学生密切合作，研究生和本科化学学生在科学活动有关的研究在Iluc集团。