Chemical and Spectroscopic Investigation of Nitrenium Ions and Related Species

氮离子及相关物质的化学和光谱研究

• 批准号: 9521601
• 负责人: Daniel Falvey
• 金额: $ 26.25万
• 依托单位: University of Maryland, College Park
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-07-01 至 1998-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9521601&HistoricalAwards=false
• 关键词: Chemical; Spectroscopic; Investigation; Nitrenium; Ions

This award is made in the Organic Dynamics Program in the support of the research of Prof. Daniel Falvey at the University of Maryland. The research deals with chemical and spectroscopic studies of nitrenium ions, photochemically generated from N-aminopyridinium salts. Two specific areas will be addressed: (1) the solution reactivity of nitrenium ions, particularly with nucleophiles, and (2) defining the structural features of nitrenium ions which control their singlet-triplet energy gaps. The former will be probed by laser flash photolysis and photothermal beam deflection calorimetry and the latter by low temperature electron paramagnetic resonance spectroscopy. Experimental studies will be complemented by semi-empirical and ab initio calculations. Nitrenium ions, as reactive intermediates in organic reactions, have not been well explored. This study of the structural features which control their singlet-triplet energy gaps, will provide fundamental information which will aid in the design of new magnetic materials. Additionally, the study of the reactivity of nitrenium ions towards nucleophiles will shed light on their role in DNA damage and carcinogenesis.

该奖项是在有机动力学项目中颁发的，以支持马里兰大学丹尼尔·法尔维教授的研究。这项研究涉及从N-氨基吡啶盐光化学产生的硝离子的化学和光谱研究。将讨论两个具体领域：(1)镍离子的溶液反应性，特别是与亲核试剂的反应性，以及(2)确定控制其单重态-三重态能隙的氮离子的结构特征。前者将通过激光闪光光解和光热偏转量热法进行研究，后者将通过低温电子顺磁共振光谱进行研究。实验研究将得到半经验和从头计算的补充。氮离子作为有机反应中的活性中间体，目前还没有得到很好的研究。对控制其单重态-三重态能隙的结构特征的研究，将为新型磁性材料的设计提供基础信息。此外，对硝离子对亲核试剂的反应性的研究将有助于阐明它们在DNA损伤和致癌中的作用。