Absolute Kinetic Studies of Carbenic Reactions

Robert A. Moss教授是新泽西州立大学罗格斯分校化学系的教授，他对碳烯和相关反应中间体的动力学研究得到了有机动力学项目的支持。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，研究烷氧基卤代烷（RO-C-Cl）的裂解反应，探索R-O和C-Cl键裂解的相关性，作为烷基取代基的函数。本研究还探讨了苄基卤代烃和-苯基乙基卤代烃的1,2- h移位重排的动力学和产物，以推断溶剂、烃类结构和卤素同一性对这些重排的Arrhenius相关性线性、可能的隧穿入侵以及同时发生的分子间反应的影响。Moss教授还研究了通过干预瞬态羰基/苯π络合物、酰基羰基和1,2-酰基（或1,2-碳）相互竞争的迁移，以及潜在的pi介导的苊基氟苯重排，来调节分子内重排和分子间捕获速率的可能性。在有机动力学项目的支持下，新泽西州立大学罗格斯分校化学系的Robert A. Moss教授开展了碳烯和相关反应中间体的动力学研究。这类化合物的中心碳原子只有两个基团，而不是更常见的（也更稳定的）四个基团，它们是在各种化学过程中瞬间形成的。通过应用快速实验技术和计算研究，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发生在许多化学反应中的基本原子水平过程，并最终提高我们控制这些反应的能力。

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.