Long & Medium Term Research: Activation and Functionaliza- tion of Chlorocarbons

长的

• 批准号: 9007698
• 负责人: Andrew Barron
• 金额: $ 3.71万
• 依托单位: Harvard University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-09-01 至 1992-02-29
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9007698&HistoricalAwards=false
• 关键词: Long; & Medium; Term; Research

Long & Medium-Term Research: Activation and Functionalization of Chlorocarbons This award recommendation is made under the Program for Long & Medium-Term Research at Foreign Centers of Excellence. The program seeks to enable U.S. scientists and engineers to conduct long-term research abroad at research institutions of proven excellence. Awards provide opportunities for the conduct of joint research, and the use of unique or compli- mentary facilities, expertise and experimental conditions in foreign countries. This award for a proposal sponsored by Dr. David A. Hoffman of Harvard University will support a twelve-month visit to France by Dr. Derk A. Wierda to work with Professeur John A. Osborn of the Institut Le Bel of the Universit> Louis Pasteur in Strasbourg on "Activation and Functionalization of Chlorocarbons." Chlorocarbons form a relatively inert class of compounds with properties which can be useful, such as solvent, or noxious, such as chlorinated aromatics (PCBs). It has recently been discovered that a series of complexes of Pd(0) will activate C-Cl bonds under mild conditions. Such complexes also serve as catalysts for the carbonylation of CH2Cl2 and C6H5Cl. The original work into chlorocarbon activation will be extended to other chloro- and polychloro- containing compounds. The researchers will conduct mechanistic studies to better understand how the process of chlorocarbon activation occurs. The will perform further research into potential catalytics reactions involving these systems. One possible reaction of interest is hydrodechlorination, a process by which chlorocarbons would be transformed into hydrocarbons. Reaction of CH2Cl2 in the presence of CO, H2, base and palladium complex catalytically generates ketene, a very reactive organic molecule. The researchers will investigate this process in the presence of various ketene traps. They will examine generation of other ketenes in situ. They shall perform investigations into the possibility of breaking the much stronger C-F bonds by similar methods. The award recommendation provides funds to cover, as appropriate, international travel, local travel abroad, stipend, dependents' allowance if applicable, and a flat administrative allowance of $250 for the U.S. home institution.

中长期研究：氯碳的活化和功能化本奖项是在国外卓越中心中长期研究计划下推荐的。该项目旨在使美国科学家和工程师能够在国外被证明卓越的研究机构进行长期研究。该奖项为开展联合研究以及利用国外独特或互补的设施、专业知识和实验条件提供了机会。这项由哈佛大学David a . Hoffman博士赞助的提案的奖金将支持Derk a . Wierda博士对法国进行为期12个月的访问，与斯特拉斯堡Louis Pasteur大学Le Bel研究所的John a . Osborn教授就“氯碳的活化和功能化”进行合作。氯碳化合物是一类相对惰性的化合物，其性质可以是有用的，如溶剂，也可以是有毒的，如氯化芳烃（pcb）。最近发现一系列的Pd(0)配合物在温和的条件下会激活C-Cl键。这类配合物也可作为CH2Cl2和C6H5Cl羰基化的催化剂。原来的工作进入氯碳活化将扩展到其他含氯和多氯化合物。研究人员将进行机理研究，以更好地了解氯碳活化过程是如何发生的。他们将进一步研究涉及这些系统的潜在催化反应。我们感兴趣的一个可能的反应是氢脱氯，在这个过程中，氯碳会转化为碳氢化合物。摘要CH2Cl2在CO、H2、碱和钯络合物的存在下催化生成烯酮，这是一种活性很强的有机分子。研究人员将在各种烯烃陷阱的存在下研究这一过程。他们将在原位检查其他酮的生成。他们将研究用类似的方法破坏更强的C-F键的可能性。奖励建议提供资金，酌情支付国际旅行，本地旅行，津贴，家属津贴（如果适用），以及美国本土机构250美元的固定行政津贴。