The Solvent Cage Effect in Organometallic Chemistry

这个项目名为“有机溶剂的笼效应 化学”将由托马斯W。Koenig和大卫R. 俄勒冈州大学的泰勒，并在 无机，生物无机和有机化学课程。 这项研究将考察有机金属自由基的命运 在溶剂笼中。这项研究的结果预计将 提高了对有机金属化合物反应性的认识 自由基，从而更好地了解机制， 许多有机金属反应发生。 研究将在笼式自由基对上进行， 由选择的前体可逆地和不可逆地形成 分子。将产生可逆形成的笼对 通过金属-金属或金属-碳键的热交换，例如在 八羰基双（三苯基膦）二锰（0）。的 不可逆形成的笼对将通过光解产生 双金属络合物，消除了一个插入原子，或 分子，如双（四羰基钴）汞，其中 汞原子作为小间隔分子被消除， 钴族。具体目标除了增加 对自由基反应性的理解是： 键离解能的显著提高值， 有机金属配合物;测定笼效率， 也就是说，与自由基的笼逃逸相比的笼组合;以及 评估自由基的空间尺寸和质量的影响， 以及溶剂的粘度对笼效率的影响。

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.