CAREER: Interconversion of Metal-Ligand Multiple Bonds. Carbenes, Carbynes, and Carbides for Metathesis and Fischer-Tropsch Modeling

职业：金属-配体多重键的相互转化。

• 批准号: 0449459
• 负责人: Marc Johnson
• 金额: $ 52.5万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-04-01 至 2010-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0449459&HistoricalAwards=false
• 关键词: CAREER; Interconversion; Metal; Ligand; Multiple

This CAREER award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor Marc Johnson at the University of Michigan to prepare late metal complexes with triple bonds to carbon or nitrogen. This project will explore the synthesis, bonding, and reactivity of late metal LnMCR and LnMN moieties. Calorimetric and computational methods will be employed to understand the energetics of species relevant to alkyne and nitrile metathesis reactions. Ruthenium carbyne, carbide, and nitrido complexes will provide access to the chemistry of late metal ligand triple bonds. A computational laboratory companion to an advanced inorganic lecture course at Michigan will be developed. Students involved with a GAANN program entitled Chemical Sciences at the Interface will collaborate with science education personnel to assess student learning outcomes in this setting.Olefin metathesis has developed into a particularly powerful tool for reconstructing complex organic molecules. In both natural product strategies and macromolecular reaction mechanisms, the impact of olefin cross reactions for new carbon-carbon bond formation is enormous. This project is designed to move toward an understanding of the principles involved in metathesis of triple bonds involving both carbon and nitrogen with transition metal complexes serving the role of mediators.

这一无机化学、生物无机化学和金属有机化学项目的职业奖支持密歇根大学的马克·约翰逊教授的工作，即制备与碳或氮三键的晚期金属络合物。本项目将探索晚期金属LnMCR和LnMN部分的合成、成键和反应活性。将使用量热和计算方法来了解与炔烃和腈的歧化反应有关的物种的能量学。碳炔、碳化物和硝基络合物将提供进入晚期金属配体三键的化学途径。密歇根大学将开发一门高级无机讲授课程的计算实验室。参与GAANN项目的学生将与科学教育人员合作，评估学生在这种环境下的学习结果。烯烃复分解已发展成为重建复杂有机分子的特别强大的工具。在天然产物策略和大分子反应机理中，烯烃交叉反应对形成新的碳-碳键的影响是巨大的。该项目旨在了解涉及碳和氮的三键歧化反应的原理，过渡金属络合物起到介体的作用。