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大学化学系的 Robert A. Moss 教授获得了有机动力学项目的支持，以进行卡宾和相关反应中间体的动力学研究。 Moss 教授使用直接光谱技术，特别是激光闪光光解，并辅以从头算分子轨道计算，研究烷氧基卤代碳烯 (RO-C-Cl) 的裂解反应，探索 R-O 和 C-Cl 键断裂的协同性与烷基取代基。 苄基卤代卡宾和 α-苯乙基卤代卡宾的 1,2-H 位移重排的动力学和产物也在探索中，以推断溶剂、卡宾结构和卤素特性对这些重排的阿累尼乌斯相关性线性的影响，可能发生隧道效应，同时发生分子间反应。 Moss 教授还研究了通过瞬时卡宾/苯 pi 络合物的干预、酰氧基卡宾中竞争性 1,2-酰基和 1,2-H（或 1,2-C）迁移来调节分子内重排和分子间捕获速率的可能性。 ，以及潜在的 pi 介导的苊基氟卡宾重排。 在有机动力学项目的支持下，新泽西州立大学罗格斯大学化学系的Robert A. Moss教授对卡宾及相关反应中间体进行了动力学研究。 此类化合物的中心碳原子仅带有两个连接基团，而不是更常见（且更稳定）的四个基团，它们在各种化学过程中瞬时形成。 通过应用快速实验技术并辅以计算研究，莫斯教授确定了各种因素对这些反应中间体化学的影响。 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级过程，并最终提高我们控制它们的能力。