Reactive Intermediates from Carbene Fragmentation

卡宾裂解反应中间体

• 批准号: 0345240
• 负责人: Robert Moss
• 金额: $ 47.93万
• 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: 2004
• 资助国家: 美国
• 起止时间: 2004-01-15 至 2009-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0345240&HistoricalAwards=false
• 关键词: Reactive; Intermediates; Carbene; Fragmentation

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.

在化学部的有机动力学计划的支持下，罗格斯大学的罗伯特·A·莫斯教授将继续对有机反应性中间体，尤其是使用直接光谱和快速动力学方法的有机反应性中间体和碳纤维化的基础研究。更具体地说，将研究碳纤维的碎片化是对具有特殊结构意义的众多碳的新颖入口。将检查形成，溶剂平衡和反应动力学的机理，并将其与从较旧的和更传统的碳分配产生方法获得的结果进行比较。离子对在杂碳碎片反应中的作用将受到仔细研究，以及均质片段化的例子。在其中一些情况下，将采用矩阵隔离方法。研究结果应增强我们诊断出极性协同碎片过渡态，紧密或接触离子对，溶剂平衡离子对以及碳纤维碎片反应中的自由基对之间的相互作用的能力。它还应有助于定义由非溶解过程产生的许多经典有机化学的经典碳的反应性和特性。有机和大分子化学计划支持罗格斯大学的罗伯特·A·莫斯教授，他们将尝试回答有关卡宾碎片化的基本问题，并检查其机制，并应用于有机系统中的碳碳，离子对或相关中间体的生成。莫斯教授将聚集一个合作者团队，他们将使用快速动力学方法，产品分析和计算方法协助回答这些问题。通过出版物和撰写学术评论文章，他将继续对物理有机化学界产生广泛的影响。莫斯教授和两位合着者将编辑反应性中间化学，该书有22章，专门针对反应性中间体的全面研究，该研究旨在针对研究生和专业化学家。