Rearrangements of Carbenes and Diazirine Excited States

卡宾和二嗪激发态的重排

• 批准号: 9613861
• 负责人: Matthew Platz
• 金额: $ 57.34万
• 依托单位: Ohio State University Research Foundation -DO NOT USE
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-02-01 至 2000-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9613861&HistoricalAwards=false
• 关键词: Rearrangements; Carbenes; Diazirine; Excited; States

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.

俄亥俄州立大学化学系的Matthew S. Platz博士得到了有机动力学项目的资助，继续他对羰基重排和偶氮嘧啶激发态的研究。他将研究由激光闪光光解氮和非氮前体生成的烷基、二烷基、环烷基和酰基碳烯，研究碳烯的结构和同位素组成、温度和溶剂极性对碳烯重排速率的影响。计算研究将解决量子力学隧道效应和动力学效应在这些重排中的可能作用。低温高分辨荧光光谱法将探讨重氮嘧啶的重排和裂解机制。新型的碳烯前体，比目前使用的更高效，将用于在低温下生成碳烯，使其能够通过紫外可见和红外光谱进行研究，并通过实验解决简单二烷基碳烯的基态电子结构问题。典型的稳定有机化合物是由碳原子与另外四个原子相连构成的，而碳烯是由碳原子与另外两个原子相连构成的，它是一种高能化合物。尽管如此，碳烯似乎是在大量的化学反应中形成的，了解它们的性质和化学性质仍然是一个重要的研究目标。Platz教授将研究几个关键变量对碳烯反应化学的影响，并将这些研究与计算工作结合起来，以评估电子结构和量子力学效应对这些反应的影响。他将制备作为碳烯前体的有机化合物，允许在允许实验研究的条件下形成通常反应性的碳烯，并将分析在世界研究界广泛使用的其他碳烯前体的化学性质，这些前体的化学性质似乎比一般认为的要复杂得多。