Organic and Organometallic Chemistry

有机和有机金属化学

• 批准号: 0841786
• 负责人: Robert Bergman
• 金额: $ 77万
• 依托单位: University of California-Berkeley
• 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: 2009-08-01 至 2014-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0841786&HistoricalAwards=false
• 关键词: Organic; Organometallic; Chemistry

The Inorganic, Bioinorganic, and Organometallic Chemistry Program supports the efforts of Dr. Robert G. Bergman of the University of California Berkeley to explore new reactions of cobalt-bound nitrosyl groups and alkenes, followed by reactions involving coordinated alkenes and other reagents. These reactions focus specifically on strained and unstrained, unsaturated hydrocarbons, so that the basic characteristics of the reactions can be most clearly elucidated. Reactions of the dinitrosyl-alkene complexes with a range of electrophiles are examined to determine the reaction components (e.g., base, Lewis acid additives) that are required to successfully form the new carbon-carbon bonds between the adducts and the electrophiles. Fundamental studies of the mechanisms of adduct formation, adduct dissociation and carbon-carbon bond forming processes include detailed kinetics and isotope labeling experiments. Particular attention is paid to understanding the role of the Lewis acid and promoter that facilitates these transformations. Parallel to the studies of the cobalt-based systems, Professor Bergman and his group are exploring whether dinitrosyl complexes involving other metals and ligands will engage in analogous chemistries with simple alkenyl derivatives. Computational methods, primarily with density functional theory, are used to predict which systems are likely to undergo reversible dinitrosyl-alkene adduct formation. Undergraduate, graduate and postdoctoral students working on this program receive excellent training. Professor Bergman has recently helped to initiate a new curriculum emphasizing science literacy for students in grades 3-5 in the local Alameda County, CA public schools.

无机化学、生物无机化学和金属有机化学计划支持加州大学伯克利分校的罗伯特·G·伯格曼博士的努力，探索钴结合的亚硝基和烯烃的新反应，随后涉及配位烯和其他试剂的反应。这些反应特别集中在应变和非应变的不饱和碳氢化合物上，因此可以最清楚地阐明反应的基本特征。研究了二亚硝基-烯烃络合物与一系列亲电体的反应，以确定成功地在加合物和亲电体之间形成新的碳-碳键所需的反应组分(例如，碱、路易斯酸添加剂)。对加合物形成、加合物解离和碳-碳键形成过程的基础研究包括详细的动力学和同位素标记实验。特别注意了解促进这些转化的Lewis酸和促进剂的作用。在研究基于钴的体系的同时，伯格曼教授和他的团队正在探索涉及其他金属和配体的二亚硝基配合物是否会与简单的烯基衍生物进行类似的化学作用。计算方法，主要是密度泛函理论，被用来预测哪些体系可能发生可逆的二亚硝基-烯烃加合物形成。在这个项目中工作的本科生、研究生和博士后都得到了很好的培训。伯格曼教授最近帮助加州阿拉米达县当地的公立学校启动了一项新课程，强调3-5年级学生的科学素养。