Late-Metal Alkyne and Metallacyclobutene Reaction Chemistry

后金属炔烃和金属环丁烯反应化学

• 批准号: 0518707
• 负责人: Joseph O'Connor
• 金额: --
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2009-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0518707&HistoricalAwards=false
• 关键词: Late; Metal; Alkyne; Metallacyclobutene; Reaction

Dr. Joseph O'Connor, Chemistry Department, University of California - San Diego, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division for an investigation of the synthesis, structural elucidation, and mechanistic aspects of the formation and reactions of metallacyclobutene complexes. A metallacyclobutene-vinylcarbene interconversion appears to play an important role in the chemistry of these species. Consequently, the factors that control the stability of the metallacyclobutenes will be studied by computational chemistry and the epimerization and acid-base chemistry of the interconversion will be investigated experimentally. New routes to metallcyclobutenes will be developed employing reactions of metal carbene complexes with diazoalkynes and thermolysis of cobalt cyclobutenes will be explored as a route to cyclopropenes. Catalytic chemistry based on pallacyclobutenes will be investigated. In addition to uncovering new synthetic approaches to and applications of these complexes, the proposed studies will address stereocontrol of their synthesis and reactions. This project involves investigations of the preparation and reactivity of a class of organometallic compound known as metallacyclobutenes. The examples of interest for these studies contain late transition elements. The major objective is the development of a mechanistic understanding of reactions that may find use in synthetic and catalytic organic chemistry. As such, the new methods will be valuable to the preparation of pharmaceuticals. The project will serve to educate and train undergraduate, graduate and postdoctoral student.

加州大学圣地亚哥分校化学系的Joseph奥康纳博士得到化学系无机、生物无机和有机化学项目的支持，研究金属环丁烯络合物的合成、结构解析和形成和反应的机理。金属环丁烯-乙烯基卡宾的相互转化似乎在这些物种的化学中起着重要的作用。因此，控制金属环丁烯的稳定性的因素将通过计算化学和差向异构化和酸碱化学的相互转化进行研究实验。利用金属卡宾络合物与重氮炔的反应，将开发新的金属环丁烯的合成路线，并探索钴环丁烯的合成路线。将研究基于钯环丁烯的催化化学。除了发现新的合成方法和这些配合物的应用，拟议的研究将解决其合成和反应的立体控制。该项目涉及一类被称为金属环丁烯的有机金属化合物的制备和反应性的研究。这些研究中感兴趣的例子包含后过渡元素。主要目标是发展一种可能在合成和催化有机化学中使用的反应的机械理解。因此，这些新方法对药物的制备具有重要价值。该项目将为本科生、研究生和博士后提供教育和培训。