Investigation of Radical Cage Effects in Organometallic Chemistry

这项由无机化学、生物无机化学和金属有机化学项目颁发的奖项支持俄勒冈大学的David Tyler教授研究自由基笼效应的基本原理，总体目标是更好地了解自由基反应性。本文将围绕笼子效应的四个方面展开研究。在一项研究中，将使用一个基于溶剂的微粘度的新模型来探索溶剂仍然令人困惑的作用。另一项研究将集中在光生自由基笼对中光波长对笼效应的影响。初步结果显示了与理论预测相反的趋势，并可能在这些实验中揭示一个新的动力学原理。第三项调查将寻求确认二次(溶剂分离)笼对的存在。已经假设二级笼对来解释自由基旋转对自由基-自由基复合反应的影响，但二级笼对还没有被明确地识别出来。最后，作为探索溶剂与溶质分子具体相互作用的研究的一部分，第四项研究将探索金属-H2络合物中H2配体的氢键如何影响H2配体的反应活性。这四项研究的结果将使研究人员深入了解笼子效应及其如何影响自由基反应。虽然研究涉及有机金属自由基，但发现的基本原理将适用于所有类型的自由基，无论是有机的、无机的还是生化的。参与该项目的研究生参加实习项目。这些创新项目通过安排博士生在地区性公司或大学进行为期一年的实习，为他们在行业或学术领域的成功职业生涯做好准备。公司和大学对该计划热情高涨，因为他们有机会与实习生合作，这些实习生拥有最新的化学、仪器、实验室技术、计算机技能和科学文献知识。该研究项目还促进了与当地公司和大学的更紧密合作关系。这导致地区性大学的教授在泰勒教授的实验室休假，俄勒冈大学化学系的外部学生使用这种仪器。在参与这项研究的研究生和本科生受众中，代表性不足的群体将有很大的影响力。

This award by the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports Professor David Tyler at the University of Oregon to investigate the fundamental, underlying principles of radical cage effects with the overall goal of better understanding radical reactivity. The research will focus on four aspects of cage effects. In one study, the still-confusing role of the solvent will be explored using a new model based on the microviscosity of the solvent. Another study will focus on what effect the wavelength of light has on the cage effect in photogenerated radical cage pairs. Preliminary results show a trend opposite to that predicted by theory, and a new principle of dynamics may be uncovered in these experiments. A third investigation will seek confirmation for the existence of secondary (solvent separated) cage pairs. Secondary cage pairs have been hypothesized to explain the effect of radical rotation on radical-radical recombination reactions but secondary cage pairs have not been unequivocally identified. Finally, as part of a study to explore how solvents specifically interact with solute molecules, a fourth study will explore how H-bonding to an H2 ligand in a metal-H2 complex can affect the reactivity of the H2 ligand. The results of these four investigations will give researchers an in-depth understanding of cage effects and how they impact radical reactivity. Although the studies involve organometallic radicals, the fundamental principles uncovered will apply to radicals of all types, whether organic, inorganic, or biochemical. Graduate students involved with this project participate in internship programs. These innovative programs prepare Ph.D. students for successful careers in industry or in academics by placing them in regional companies or in colleges for a one-term internship experience. Companies and colleges are enthusiastic about the program because they have the opportunity to work with interns who have an up-to-date knowledge of chemistry, instrumentation, laboratory techniques, computer skills, and the scientific literature. The research program also fosters closer collaborative ties with local companies and colleges. This has led to professors at regional colleges taking sabbatical leaves in Professor Tyler's lab and to outside students using the instrumentation in the University of Oregon Chemistry Department. Underrepresented groups will have a strong presence in the graduate and undergraduate student audience that participates in the research.