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.

Robert A.罗格斯大学化学系的莫斯说， 新泽西的州立大学，是由有机动力学的支持 卡宾及相关反应动力学研究计划 中间体的 莫斯教授使用直接光谱技术， 特别是激光闪光光解， 轨道计算，研究碎片化反应， 烷氧基卤代卡宾（RO-C-Cl），探索R-O和C-Cl的协同作用 键断裂作为烷基取代基的函数。 的动力学和 苄基卤代卡宾的1，2-H移位重排产物， α-苯乙基卤代卡宾也在探索中， 推导出溶剂、卡宾结构和卤素特性对反应的影响 关于这些重排的阿克里尼乌斯相关性的线性， 隧道的可能入侵，以及同时发生的 分子间反应 莫斯教授还调查了 调节分子内重排速率的可能性， 瞬态卡宾/苯介入的分子间捕获 π络合物，竞争1，2-酰基和1，2-H（或1，2-C）迁移， 酰氧基卡宾，和潜在的π介导的重排， 苊基氟卡宾。 在有机动力学项目的支持下，罗伯特·A· 莫斯说，罗格斯大学化学系的，州立大学， 新泽西，进行卡宾和相关反应的动力学研究 中间体的 这类化合物含有一个中心碳原子， 只有两个连接组，而不是更常见的（和更多） 稳定）四种，在多种化学物质中瞬时形成 流程. 通过应用快速实验技术 通过计算研究的补充，莫斯教授确定 各种因素对这些反应性化学的影响 中间体的 这些研究有助于我们了解 许多化学反应中发生的基本原子水平过程 并最终影响到我们控制它们的能力