Rearrangements of Carbenes and Diazirine Excited States

Matthew S.博士俄亥俄州化学系广场 大学由有机动力学计划的赠款支持， 继续研究卡宾和激发态的重排 二氮杂环丙烷。 他将研究烷基、二烷基、环烷基和酰基 激光闪光光解含氮和 非含氮前体，考察卡宾结构的影响 同位素组成、温度和溶剂极性对反应速率的影响 卡宾重排反应 计算研究将解决 量子力学隧道效应和动力学效应在量子力学中的可能作用 这些重组。 重排和裂解机制 二氮杂环丙烷将通过低温高分辨率荧光探测 谱 新型卡宾前体，比那些 目前使用的，将用于在低温下产生卡宾， 允许通过紫外可见和红外光谱对其进行研究， 通过实验研究基态电子结构 简单的二烷基卡宾。 与典型的稳定有机化合物相比， 碳原子连接到其他四个原子，卡宾，其中包含 碳只与另外两个原子结合，是高能化合物。 尽管如此，卡宾似乎是在大量的化学物质中形成的。 反应，并了解其性质的发展， 化学仍然是一个重要的研究目标。 普拉茨教授将研究 几个关键变量对反应化学的影响 并将这些研究与计算工作相结合， 来评估电子结构和量子力学 对这些反应的影响。 他将制备有机化合物， 作为卡宾的前体，允许形成通常的 反应性卡宾在允许其实验研究的条件下， 并将分析其他广泛使用的卡宾前体的化学性质， 在整个世界研究界，这似乎显示出更多的 比一般理解的复杂化学。

Dr. Matthew S. Platz of the Department of Chemistry at Ohio State University is supported by a grant from the Organic Dynamics Program to continue his studies of the rearrangements of carbenes and excited states of diazirines. He will study alkyl, dialkyl, cycloalkyl, and acyl carbenes generated by laser flash photolysis of nitrogenous and non-nitrogenous precursors, examining the influence of carbene structure and isotopic composition, temperature, and solvent polarity on the rate of carbene rearrangement. Calculational studies will address the possible roles of quantum mechanical tunneling and dynamical effects in these rearrangements. Rearrangement and cleavage mechanisms of diazirines will be probed by low-temperature high resolution fluorescence spectroscopy. New types of carbene precursors, more efficient than those currently used, will be used to generate carbenes at low temperature, allowing their study by UV-visible and infrared spectroscopy and experimentally addressing the issue of ground state electronic structure for simple dialkyl carbenes. In contrast to typical stable organic compounds, which are based on carbon atoms connected to four other atoms, carbenes, which contain carbon bonded to only two other atoms, are high-energy compounds. None-the-less, carbenes appear to be formed in a large number of chemical reactions, and development of an understanding of their properties and chemistry remains an important research goal. Professor Platz will study the influence of several critical variables on the reaction chemistry of carbenes and will couple these studies with calculational work in order to assess the influence of electronic structure and quantum mechanical effects on these reactions. He will prepare organic compounds which serve as precursors to carbenes, allowing the formation of ordinarily reactive carbenes under conditions which permit their experimental study, and will analyze the chemistry of other carbene precursors, widely used throughout the world research community, which appear to display more complex chemistry than generally appreciated.