Absolute Kinetic Studies of Carbenic Reactions

卡宾反应的绝对动力学研究

• 批准号: 9710547
• 负责人: Robert Moss
• 金额: $ 44.09万
• 依托单位: Rutgers University New Brunswick
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-01-01 至 2001-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9710547&HistoricalAwards=false
• 关键词: Absolute; Kinetic; Studies; Carbenic; Reactions

Professor Robert A. Moss, of the Department of Chemistry at Rutgers, the State University of New Jersey, is supported by the Organic Dynamics Program for his kinetic studies of carbenes and related reactive intermediates. Professor Moss uses direct spectroscopic techniques, particularly laser flash photolysis, complemented by ab initio molecular orbital calculations, to study the fragmentation reactions of alkoxyhalocarbenes (RO-C-Cl), exploring the concertedness of R-O and C-Cl bond cleavages as a function of the alkyl substituent. The kinetics and products of the 1,2-H shift rearrangements of benzylhalocarbenes and alpha-phenylethylhalocarbenes are also under exploration in order to deduce the influences of solvent, carbene structure, and halogen identity on the linearity of the Arrhenius correlations for these rearrangements, the possible incursion of tunneling, and the simultaneous occurrence of intermolecular reactions. Professor Moss also investigates the possibility of modulating the rates of intramolecular rearrangements and intermolecular capture by the intervention of transient carbene/benzene pi complexes, competing 1,2-acyl and 1,2-H (or 1,2-C) migrations in acyloxycarbenes, and the potentially pi-mediated rearrangement of acenaphthenylfluorocarbene. With the support of the Organic Dynamics Program, Professor Robert A. Moss, of the Department of Chemistry at Rutgers, the State University of New Jersey, carries out kinetic studies of carbenes and related reactive intermediates. Such compounds, containing a central carbon atom bearing only two attached groups rather than the more commonly seen (and more stable) four, are formed transiently in a wide variety of chemical processes. Through the application of fast experimental techniques complemented by calculational studies, Professor Moss determines the effects of various factors on the chemistry of these reactive intermediates. These studies contribute to our understanding of the fundamental atomic level processes occurring in many chemical reactions and, ultimately, to our ability to control them.

新泽西州立大学罗格斯化学系的罗伯特·A·莫斯（Robert A. Moss）教授得到了有机动力学计划的支持。 Moss教授使用直接光谱技术，尤其是由Ab Insibul Mocular Orbital计算补充的激光闪光分解，以研究烷氧基甲苯甲酸（RO-C-CL）的碎片反应，探索R-O和C-C-CL键合的协调性和C-C-CL键合的性质，并作为烷基替代物的功能。 为了推断溶剂，碳烯结构和卤素对等类似的偏移趋势的影响，氧化甲苯和α-苯基甲基甲基苯甲酸的1,2-H偏移重排的动力和产物也正在探索。分子间反应。 莫斯教授还研究了通过短暂的碳/苯PI复合物的干预，竞争1,2-acyl和1,2-H（OR 1,2-C）在acyloxycarbenes中迁移的抗分子内重排和分子间捕获的可能性。 在有机动力学计划的支持下，新泽西州立大学罗格斯化学系的罗伯特·A·莫斯（Robert A. 这种化合物，含有中央碳原子，只有两个附着的基团，而不是更常见的（更稳定）的四种，在各种化学过程中瞬时形成。 通过计算研究补充的快速实验技术的应用，Moss教授确定了各种因素对这些反应性中间体化学的影响。 这些研究有助于我们理解许多化学反应中发生的基本原子水平过程，并最终有助于我们控制它们的能力。