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.

在化学系有机动力学项目的支持下，罗格斯大学的 Robert A. Moss 教授将继续使用直接光谱和快速动力学方法对有机反应中间体，特别是卡宾和碳正离子进行基础研究。更具体地说，卡宾的裂解将作为研究具有特殊结构意义的众多碳正离子的新途径进行研究。将检查形成机制、溶剂平衡和反应动力学，并与较旧和更传统的碳正离子生成方法获得的结果进行比较。将仔细研究离子对在异解卡宾碎裂反应中的作用以及均裂碎裂的例子。在其中一些情况下将采用矩阵隔离方法。研究结果应提高我们诊断卡宾裂解反应中极性协同裂解过渡态、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。它还有助于定义由非溶剂分解过程产生的物理有机化学的许多经典碳阳离子的反应性和性质。有机和高分子化学项目支持罗格斯大学的 Robert A. Moss 教授，他们将尝试回答有关卡宾碎裂的基本问题，并研究其机制以及在有机系统中生成碳阳离子、离子对或相关中间体的应用。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。他将通过出版物和撰写学术评论文章传播他的研究成果，继续对物理有机化学界产生广泛影响。 Moss 教授与两位合著者将编辑《Reactive Intermediate Chemistry》一书，该书共有 22 章，专门针对研究生和专业化学家全面研究反应中间体。