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

无机、生物无机和有机金属化学项目的CAREER奖支持密歇根大学Marc Johnson教授制备与碳或氮有三键的晚期金属配合物的工作。本项目将探索晚期金属LnMCR和LnMN基团的合成、成键和反应性。量热法和计算方法将被用来了解与炔和腈复分解反应相关的物质的能量学。碳化钌、碳化物和氮络合物将提供晚期金属配体三键的化学途径。一个计算实验室将与密歇根大学的高级无机讲座课程相结合。参与GAANN项目“界面上的化学科学”的学生将与科学教育人员合作，评估学生在这种情况下的学习成果。烯烃复分解已发展成为重建复杂有机分子的一种特别有力的工具。在天然产物策略和大分子反应机制中，烯烃交叉反应对新碳-碳键形成的影响是巨大的。该项目旨在了解涉及碳和氮的三键复合的原理，过渡金属配合物作为介质的作用。

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.