Gas-Phase Studies of Substituted Aromatic Radicals, Biradicals and Polyradicals

取代芳族自由基、双自由基和多自由基的气相研究

• 批准号: 9710456
• 负责人: Hilkka Kenttamaa
• 金额: $ 32.8万
• 依托单位: Purdue Research Foundation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-08-01 至 2000-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9710456&HistoricalAwards=false
• 关键词: Gas; Phase; Studies; Substituted; Aromatic

With the support of the Organic Dynamics Program and the Office of Multidisciplinary Activities of the Mathematical and Physical Sciences Directorate, Professor Hilkka I. Kenttamaa, of the Department of Chemistry at Purdue University, carries out gas-phase studies of substituted aromatic radicals, biradicals, and polyradicals. By generating aromatic radicals which incorporate a positively charged group, Professor Kenttamaa is able to employ Fourier-transform ion cyclotron resonance mass spectrometry to examine their intrinsic or solvent-free reactivity under clean conditions, permitting the assessment of reaction rate constants, product branching ratios, and thermochemical parameters such as bond dissociation energies. Substituent effects are explored for phenyl, benzyl, and other aromatic mono- and polyradicals carrying neutral substituents in addition to the remote charged groups, and radical traps are employed to probe the importance of polar effects in different types of radical reactions. For biradicals, the relationship between reactivity and predicted ground state multiplicity is examined, and this information is used to search for spin-selective gas-phase reactions. Professor Hilkka I. Kenttamaa, of the Department of Chemistry at Purdue University, with the support of the Organic Dynamics Program and the Office of Multidisciplinary Activities of the Mathematical and Physical Sciences Directorate, studies the chemistry of molecules containing one or more unpaired electrons (`radicals`). By appropriate choice of radicals, Professor Kenttamaa is able to employ gas-phase techniques to study their formation and reactivity, permitting an assessment of their intrinsic properties in the absence of the complicating influences of solvents or other potentially reactive species. Through these studies is gained fundamental knowledge regarding the chemistry of electron-deficient molecules, advancing the understanding of the roles of substituent effects and polar effects in governing their reactivity and offering potential advances in the areas of radical-based organic synthesis and organic materials research.

在Purdue University的化学系的数学和物理科学局的多学科活动的支持下，Hilkka I. Kenttamaa教授在Purdue University的化学局的跨学科活动办公室的支持下进行了替代的芳香自由基，Biradicals和Colyardadicals的气相研究。 通过产生芳香的自由基，并结合了一个带电的群体，Kenttamaa教授能够采用傅立叶转换离子回旋共振质谱法检查其在清洁条件下的内在或无溶剂无反应性，从而允许评估反应速率常数，产物分支比率，产物分支比率，产物分支比率，并热化型号型号分解型脱节型。 除了远程带电组外，还探索了苯基，苄基和其他携带中性取代基的苯基，苄基和其他芳族单子和多性自由基的作用，并采用自由基陷阱来探测不同类型的自由基反应中极性效应的重要性。 对于Biradical，检查了反应性与预测的基态多样性之间的关系，该信息用于搜索自旋选择性气相反应。 普渡大学化学系的Hilkka I. Kenttamaa教授在有机动力学计划和数学和物理科学局的多学科活动办公室的支持下，研究了包含一个或多个不成对电子的分子化学（``Radicals）。 通过适当的自由基选择，肯塔玛教授能够采用气相技术来研究其形成和反应性，从而在没有溶剂或其他潜在反应性物种的复杂影响的情况下评估其内在特性。 通过这些研究，获得了有关电子缺陷分子化学的基本知识，从而促进了对取代基效应的作用以及极性效应在控制其反应性和在基于自由基的有机合成和有机材料研究领域的潜在进步方面的理解。