Absolute Kinetic Studies of Carbenic Reactions

新泽西州立大学罗格斯大学化学系的罗伯特·A·莫斯教授因其对卡宾和相关活性中间体的动力学研究而得到有机动力学计划的支持。Moss教授使用直接光谱技术，特别是激光闪光光解，辅以从头算分子轨道计算，研究了烷氧基卤代卡宾(RO-C-Cl)的裂解反应，探索了R-O和C-Cl键断裂作为烷基取代基的函数。1，2-H转移重排的动力学和产物也在探索中，以推断溶剂、卡宾结构和卤素同一性对这些重排的Arrhenius关联式的线性、可能的隧道入侵和分子间反应的同时发生的影响。莫斯教授还研究了通过干预瞬时卡宾/苯pi络合物、酰氧卡宾中竞争的1，2-酰基和1，2-H(或1，2-C)迁移以及潜在的pi介导的并烯基氟卡宾的重排来调节分子内重排和分子间捕获的可能性。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罗伯特·A·莫斯教授对卡宾和相关的活性中间体进行了动力学研究。这类化合物含有一个中心碳原子，只有两个连接的基团，而不是更常见(也更稳定)的四个基团，在各种化学过程中瞬时形成。通过应用快速实验技术并辅之以计算研究，莫斯教授确定了各种因素对这些活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。

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.