Reactive Bi-Metallic Early-Late-Transition Metal Complexes: Preparation, Structure, Dynamics and Reactivity of ThermallyStable Early-Transition Metal Allyl Halide Compounds

无机、生物无机和有机金属化学项目支持涉及早期过渡金属化合物的合成、结构、动力学和反应性的基础研究。这一领域的研究对由二氧化碳制成的合成燃料具有重要意义。本项目申请资金支持合成有机金属的研究，以制备具有甲基化烯丙基配体和卤化物配体的热稳定和高活性的早期过渡金属配合物。这些新化合物将允许用烯丙基配体取代杂金属早-晚过渡金属配合物中普遍存在的环戊二烯基配体。这种异质金属还没有表现出人们所希望的那种双金属协同反应性，比如二氧化碳络合。通过在这些配合物中用烯丙基配体取代Cp配体，在早期过渡金属中心的反应性和真正的早期-晚期过渡金属协同性应该第一次实现。本研究项目的主要工作是制备、操作和表征新的空气敏感的早期过渡金属烯丙基配合物，全部由霍普学院的本科生研究人员完成，他们参与了学期和夏季的研究。

The Inorganic, Bioinorganic and Organometallic Chemistry Program supports basic research which involves synthesis, structure, dynamics and reactivity of early transition metal compounds. This area of research has significance to synthetic fuels made from carbon dioxide. This project requests funds to support synthetic organometallic research to prepare thermally stable and highly reactive early-transition metal complexes possessing both methylated allyl ligands and halide ligands. These new compounds will allow replacement of the ubiquitous cyclopentadienyl ligand with allyl ligands in heterometallic early-late-transition metal complexes. Such heterometallics have not yet demonstrated the kind of cooperative bimetallic reactivity that has been hoped, such as CO2 complexation. By replacing Cp ligands with allyl ligands in these complexes, reactivity at the early-transition metal center and the first instance of true early-late-transition metal cooperativity should be achieved. The main efforts of this research project, the preparation, manipulation, and characterization of new air-sensitive early-transition metal allyl complexes, are being performed entirely at Hope College by undergraduate researchers involved in semester and summer research.