The Solvent Cage Effect in Organometallic Chemistry

有机金属化学中的溶剂笼效应

• 批准号: 8815745
• 负责人: Thomas Koenig
• 金额: $ 15.78万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-01-01 至 1992-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8815745&HistoricalAwards=false
• 关键词: Solvent; Cage; Effect; Organometallic; Chemistry

This project titled "The Solvent Cage Effect in Organometallic Chemistry" will be carried out by Thomas W. Koenig and David R. Tyler of the University of Oregon and is funded within the Inorganic, Bioinorganic and Organometallic Chemistry Program. The research will examine the fate of organometallic radicals in a solvent cage. The results of this study are expected to lead to enhanced knowledge of the reactivity of organometallic radicals and thus a greater understanding of the mechanism by which many organometallic reactions occur. Studies will be carried out on cage radical pairs that are formed both reversibly and irreversibly from selected precursor molecules. The reversibly formed cage pairs will be generated by thermolysis of metal-metal or metal-carbon bonds, such as in octacarbonylbis(triphenylphosphine)dimanganese(0). The irreversibly formed cage pairs will be generated by photolysis of dimetallic complexes which eliminate an intervening atom or molecule, such as bis(tetracarbonylcobalt)mercury in which the mercury atom is eliminated as the small spacer molecule between the cobalt groups. Specific goals in addition to the increased understanding of radical reactivity are: determining substantially improved values of bond dissociation energies for organometallic complexes; determining the cage efficiency, i.e., cage combination compared to cage escape of radicals; and assessing the effects of steric size and mass of the radical as well as the viscosity of the solvent on the cage efficiency.

这个名为“有机金属化学中的溶剂笼效应”的项目将由俄勒冈大学的 Thomas W. Koenig 和 David R. Tyler 进行，并由无机、生物无机和有机金属化学项目资助。 该研究将研究有机金属自由基在溶剂笼中的命运。这项研究的结果预计将增强对有机金属自由基反应性的了解，从而更好地理解许多有机金属反应发生的机制。 将对由选定的前体分子可逆和不可逆形成的笼自由基对进行研究。可逆形成的笼对将通过金属-金属或金属-碳键的热解产生，例如在八羰基双(三苯基膦)二锰(0)中。不可逆形成的笼对将通过双金属络合物的光解产生，其消除中间原子或分子，例如双(四羰基钴)汞，其中汞原子作为钴基团之间的小间隔分子被消除。除了加深对自由基反应性的了解之外，具体目标还有：确定有机金属配合物的键解离能的显着改进值；确定笼效率，即笼组合与自由基的笼逃逸相比；并评估自由基的空间大小和质量以及溶剂的粘度对笼效率的影响。