Novel Electrophilic Carbene Architectures and Related Main Group Analogs

新型亲电卡宾结构和相关主族类似物

基本信息

批准号：
1955396
负责人：
Todd Hudnall
金额：
$ 45万
依托单位：
Texas State University - San Marcos
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-05-15 至 2024-04-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955396&HistoricalAwards=false
关键词：
Novel Electrophilic Carbene Architectures Related

项目摘要

Carbon is the building material upon which the elements of life are constructed. A basic tenet is that carbon forms four chemical bonds. In this project, funded by the Chemical Synthesis Program of the Chemistry Division, Professor Todd Hudnall of the Department of Chemistry and Biochemistry at Texas State University - San Marcos seeks to prepare substances that violate the four-bonds per carbon principle. Specifically, compounds called carbenes that contain carbon with only two bonds are prepared. Because of the unusually low number of bonds, carbenes are very reactive and have important electronic properties. The methods that are developed to prepare the carbenes are extended to the related elements, germanium and tin. These synthetic methods potentially useful, low temperature ways to access metastable alloys. In addition to training undergraduate and graduate students, this project may ultimately result in the discovery of novel materials that may benefit society in applications ranging from quantum computing to single molecular magnets to catalysts. Professor Hudnall has maintained a collaborative outreach program with the McKenna Children’s Museum called “Laboratory Workstations.” This program engages children, ages 3-10, in hands-on simple chemistry experiments in mock gloveboxes, and is also inclusive of local chemistry students from Canyon High School. Texas State University is an Hispanic Serving Institution. This project provides research experiences to students from groups underrepresented in science. The aim of this project is to prepare electrophilic carbene ligands and related main group analogs. Sets of carbenes, whose electrophilic character and attendant pi-acidity can be systematically increased by a lowering of their respective Lowest Unoccupied Molecular Orbital (LUMO) energy levels, are targeted using computations. These compounds and related germanium and tin species with exceptionally small singlet-triplet gaps are prepared. Among these are diamidosilylenes, germylenes, stannylenes, and cationic heterocyclic carbenes. One question that is investigated is why diamidocarbenes can be photolyzed to a triplet excited state where other carbenes cannot. The photochemistry of the carbenes is explored and applications as electrophilic carbene-supported main group catalysts and as precursors for the low-temperature generation of main group alloys are developed. The program serves students from underrepresented groups by their inclusion in the research project and though outreach programs to K-12 students.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.

碳是建造生命元素的建筑材料。一个基本的宗旨是碳形成四个化学键。在该项目中，由化学部的化学合成计划资助，得克萨斯州立大学化学和生物化学系的托德·哈德纳尔教授 - 圣马科斯试图准备违反每碳原理四个键的物质。具体而言，称为含有碳的碳纤维的化合物仅制备了两个键。由于键的数量很少，因此碳纤维具有反应性，具有重要的电子特性。制备碳纤维的方法扩展到相关元素，锗和锡。这些合成方法可能有用，低温访问可稳定合金的方法。除了培训本科生和研究生培训外，该项目最终可能会发现新型材料，这些新材料可能使社会受益于从量子计算到单分子磁铁再到催化剂的应用。哈德纳尔教授与麦肯纳儿童博物馆（McKenna Children's Museum）保持了合作推广计划，称为“实验室工作站”。该计划与3-10岁的儿童在模拟手套箱中进行了简单的化学实验，还包括来自峡谷高中的当地化学学生。德克萨斯州立大学是西班牙裔服务机构。该项目为科学领域人数不足的小组的学生提供了研究经验。该项目的目的是制备亲电碳纤维配体和相关的主要组类似物。通过计算，可以使用计算来靶向一组碳纤维，它们的亲电性和随之而来的pi-acerivity可以系统地提高其各自的最低分子轨道（Lumo）能级。这些化合物以及相关的锗和锡物种具有非常小的单线缝隙。其中包括二氨基甲硅烷基烯，生殖器，stannylenes和阳离子杂环碳纤维。一个研究的一个问题是，为什么可以将二氨二卡苯二甲苯丙烯转化为其他碳纤维不能的三胞胎激发态。探索了碳纤维的光化学，并用作电池碳纤维的主要组催化剂的应用，并开发了低温生成主要组合金的前体。该计划通过将其包含在研究项目中，并向K-12学生提供外展计划为来自代表性不足的团体的学生提供服务。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响来评估，被认为是宝贵的支持。