Reactive Intermediates from Carbene Fragmentation

在化学系有机动力学项目的支持下，罗格斯大学的罗伯特·A·莫斯教授将继续使用直接光谱和快速动力学方法对有机活性中间体，特别是卡宾和碳正离子进行基础研究。更具体地说，卡宾的裂解将作为许多具有特殊结构意义的碳正离子的新条目而被研究。将考察生成机理(S)、溶剂平衡和反应动力学，并将其与更古老和更传统的碳正离子生成方法所获得的结果进行比较。离子对在异源裂解卡宾裂解反应中的作用以及均裂解裂解的例子将被仔细研究。在其中一些情况下，将采用矩阵隔离方法。这些研究结果将增强我们诊断卡宾裂解反应中极性协同碎裂过渡态、紧密或接触离子对、溶剂平衡离子对和自由基对之间相互作用的能力。它还应该有助于确定由非溶剂化过程产生的许多经典的物理有机化学碳正离子的反应性和性质。有机与高分子化学计划支持罗格斯大学的罗伯特·A·莫斯教授，他将试图回答关于卡宾裂解的基本问题，并研究其机制(S)及其在有机体系中生成碳正离子、离子对或相关中间体的应用。莫斯教授将召集一组合作者，他们将使用快速动力学方法、产品分析和计算方法帮助回答这些问题。他将继续通过出版和撰写学术评论文章来传播他的研究结果，从而对物理有机化学界产生广泛的影响。莫斯教授和两位合著者将编辑《活性中间体化学》，这本书有22章，致力于对活性中间体的全面研究，面向研究生和专业化学家。

With the support of the Organic Dynamics Program in the Chemistry Division, Professors Robert A. Moss of Rutgers University will continue fundamental studies of organic reactive intermediates, particularly carbenes and carbocations using direct spectroscopic and fast kinetics methodologies. More specifically, the fragmentation of carbenes will be studied as a novel entry to numerous carbocations of special structural significance. Mechanism(s) of formation, solvent equilibration, and the kinetics of reaction will be examined and compared with results obtained from older and more traditional methods of carbocation generation. The role of ion pairs in heterolytic carbene fragmentation reactions will be closely examined as well as examples of homolytic fragmentation. Matrix isolation methods will be employed in some of these cases. The research results should enhance our ability to diagnose the interplay between polar concerted fragmentation transition states, tight or contact ion pairs, solvent equilibrated ion pairs, and radical pairs in carbene fragmentation reactions. It should also contribute to defining the reactivity and properties of many of the classic carbocations of physical organic chemistry as generated by a non-solvolytic procedure. The Organic and Macromolecular Chemistry Program supports Professors Robert A. Moss of Rutgers University who will attempt to answer fundamental questions on carbene fragmentation, and examining its mechanism(s) and application to the generation of carbocations, ion pair, or related intermediates in organic systems. Professor Moss will gather a team of collaborators who will assist in answering these questions using fast kinetics methodology, product analysis and computational methods. He will continue to have a broad impact on the physical organic chemistry community by distributing the results of his research through publications and writing scholarly review articles. Professor Moss along with two co-authors will edit Reactive Intermediate Chemistry, a book of 22 chapters devoted to a comprehensive study of reactive intermediates that is intended for graduate students and professional chemists.