Fundamental Chemistry of Carbenes and Diazirines

卡宾和二氮丙啶的基础化学

• 批准号: 0840995
• 负责人: Robert Moss
• 金额: $ 67.4万
• 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: 2009
• 资助国家: 美国
• 起止时间: 2009-06-01 至 2014-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0840995&HistoricalAwards=false
• 关键词: Fundamental; Chemistry; Carbenes; Diazirines

The Organic and Macromolecular Chemistry Program in the Chemistry Division at the National Science Foundation supports Professor Robert A. Moss of Rutgers University who will study carbenes, diazirines, and other reactive species by fast and ultrafast spectroscopic methods. These studies are intended to correlate molecular structure with the reaction channels of highly reactive, short-lived organic intermediates. Novel syntheses will also be developed for diazirine precursors of carbenes. Target areas will include the measurement of activation parameters for carbene-alkene additions and the interplay of enthalpy and entropy in these additions; spectroscopic studies of carbene solvation; and the chemistry of incarcerated carbenes. Difluorocarbene will be generated from difluorodiazirine, and the absolute kinetics of its additions to alkenes will be determined. Activation parameters for alkene additions will be measured by nanosecond laser flash photolysis (LFP) for phenylchlorocarbene, dichlorocarbene, fluorochlorocarbene, methoxychlorocarbene, phenylfluorocarbene, difluorocarbene, methoxyfluorocarbene, methylmethoxycarbene, phenylmethoxycarbene, and dimethoxycarbene. A fundamental and synoptic picture of carbene-alkene addition reactions will be constructed and parallel computational studies will be conducted.Research by Professor Moss in the previous award period has contributed to the training of five undergraduates (2 females, 3 males), three graduate students (2 females and one African American), and six postdoctoral students (one female, 5 males). In addition to the training of a diverse group of students, Professor Moss has produced scholarly reviews that permit amplification of his NSF-sponsored research and thus reach a wider segment of the chemical community. During his most recent grant period, he published two well-received, co-edited books on the chemistry of reactive intermediates. In addition, he authored four reviews dealing with the chemistry of singlet carbenes; the synthesis of diazirines; SNi fragmentation reactions; and new mechanisms in carbene and diazirine chemistry. The publication of scholarly reviews will continue, with future topics to include the fragmentation of carbenes, the interplay of enthalpy and entropy in carbene-alkene additions, and the synthesis of dihalodiazirines.

美国国家科学基金会化学部的有机和高分子化学项目支持罗格斯大学的 Robert A. Moss 教授，他将通过快速和超快光谱方法研究卡宾、二氮丙啶和其他活性物质。这些研究旨在将分子结构与高活性、短寿命有机中间体的反应通道联系起来。还将开发卡宾的二氮丙啶前体的新合成方法。目标领域将包括卡宾-烯烃加成的活化参数的测量以及这些加成中的焓和熵的相互作用；卡宾溶剂化的光谱研究；以及监禁卡宾的化学性质。二氟卡宾将从二氟二氮丙啶生成，并且将确定其加成到烯烃的绝对动力学。烯烃加成的活化参数将通过纳秒激光闪光光解（LFP）测量苯基氯卡宾、二氯卡宾、氟氯卡宾、甲氧基氯卡宾、苯基氟卡宾、二氟卡宾、甲氧基氟卡宾、甲基甲氧基卡宾、 苯基甲氧基卡宾和二甲氧基卡宾。将构建卡烯-烯烃加成反应的基本概况图，并进行并行计算研究。Moss教授在上一奖项期间的研究已培养了五名本科生（2名女性、3名男性）、3名研究生（2名女性和1名非裔美国人）和6名博士后（1名女性、5名男性）。除了培训不同的学生群体外，莫斯教授还撰写了学术评论，以扩大他由国家科学基金会资助的研究，从而影响化学界更广泛的领域。在他最近的资助期间，他出版了两本广受好评的共同编辑的关于反应中间体化学的书籍。此外，他还撰写了四篇有关单线态卡宾化学的评论；二氮丙啶的合成； SNi碎裂反应；以及卡宾和二氮丙啶化学的新机制。学术评论将继续发表，未来的主题包括卡宾的碎裂、卡宾-烯烃加成中的焓和熵的相互作用以及二卤二氮丙啶的合成。