Fundamentals and Analytical Applications of Hypervalent Radical Chemistry

超价自由基化学的基础和分析应用

• 批准号: 9102442
• 负责人: Frantisek Turecek
• 金额: $ 16.35万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-04-15 至 1994-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9102442&HistoricalAwards=false
• 关键词: Fundamentals; Analytical; Applications; Hypervalent; Radical

With support from the Organic Dynamics Program, Dr. Turecek will investigate the preparations, stabilities, and dissociations of hypervalent oxonium, ammonium, and sulfonium radicals that are generated and analyzed via neutralization- reionization mass spectrometry. In addition, fragmentations of neutral species will be employed for the structural elucidation of complex organic compounds by mass spectrometry. %%% Hypervalent radicals represent a class of unstable species in which the formal valence of an atom exceeds its normal coordination number in the given oxidation state. Dissociations of small hypervalent radicals often display deuterium (H-2) and O-18 isotope effects of unusual magnitude; the nature of these effects is not well understood. Dr. Turecek will study hypervalent radicals in the gas phase by employing the recently developed technique of neutralization reionization mass spectrometry. In the gas phase, hypervalent radicals can undergo exothermic dissociations to afford stable products. Thus, these species hold promise as a novel method by which mass spectroscopy can be used for organic structural analysis.

在有机动力学计划的支持下，Turecek 博士将研究通过中和-再电离质谱法产生和分析的高价氧自由基、铵自由基和锍自由基的制备、稳定性和解离。此外，中性物质的碎片将用于通过质谱分析复杂有机化合物的结构。 %%% 高价自由基代表一类不稳定的物质，其中原子的形式化合价超过其在给定氧化态下的正常配位数。小的高价自由基的解离通常表现出异常程度的氘 (H-2) 和 O-18 同位素效应；这些影响的本质尚不清楚。 Turecek 博士将通过采用最近开发的中和再电离质谱技术来研究气相中的高价自由基。在气相中，高价自由基可以发生放热解离以提供稳定的产物。 因此，这些物质有望成为一种利用质谱法进行有机结构分析的新方法。