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

长期和中期研究：氯碳化合物的活化和功能化这个奖项的推荐是根据外国英才中心的长期和中期研究计划提出的。该计划旨在使美国科学家和工程师能够在国外被证明是优秀的研究机构进行长期研究。奖项提供了开展联合研究的机会，并利用外国独特或配套的设施、专门知识和实验条件。该奖项由哈佛大学的大卫·A·霍夫曼博士发起，将支持德克·A·维尔达博士对法国为期12个月的访问，与斯特拉斯堡勒贝尔大学路易斯·巴斯德研究所的约翰·A·奥斯本教授合作，研究氯碳化合物的活化和功能化。氯代烃形成了一类相对惰性的化合物，其性质可能是有用的，如溶剂，也可能是有毒的，如氯化芳香烃(PCB)。最近发现，在温和的条件下，一系列Pd(0)的络合物可以激活C-Cl键。此类络合物还可用作CH2Cl2和C6H5Cl的羰化反应的催化剂。最初关于氯碳活化的工作将扩展到其他含氯和多氯的化合物。研究人员将进行机制研究，以更好地了解氯碳活化过程是如何发生的。他们将对涉及这些体系的潜在催化反应进行进一步研究。一个可能感兴趣的反应是加氢脱氯，这是一个将氯碳化物转化为碳氢化合物的过程。CH2Cl2在CO、H2、碱和钯配合物存在下的反应催化生成酮，这是一种非常活跃的有机分子。研究人员将在存在各种烯酮陷阱的情况下研究这一过程。他们将在现场检查其他烯烃的生成情况。他们将对用类似方法打破更强的C-F键的可能性进行调查。奖励建议提供资金，酌情支付国际旅行、当地出国旅行、津贴、受抚养人津贴(如果适用)，以及为美国本土机构提供250美元的固定行政津贴。

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.