Synthetic, Structural, and Mechanistic Studies of Organo- metallic Compounds Derived from Three-Membered Organic Rings

三元有机环衍生的有机金属化合物的合成、结构和机理研究

• 批准号: 9224467
• 负责人: Russell Hughes
• 金额: $ 26.4万
• 依托单位: Dartmouth College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-05-15 至 1997-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9224467&HistoricalAwards=false
• 关键词: Synthetic; Structural; Mechanistic; Studies; Organo

With the support of this award in the Inorganic, Bioinorganic, and Organometallic Program, Dr. Russell P. Hughes of the Chemistry Department, Dartmouth College, would continue investigations on the cleavage and formation of carbon-carbon bonds promoted by transition metals. Three projects would be pursued: ring-opening in vinylcyclopropene rearrangements; characterization of eta-3-cyclopropenyl complexes, including their CO substitution reactions and rotation barriers; and bond cleavage of sterically destabilized cyclopentadienyl ligands. The latter reactions do not proceed by simple metal insertion into the carbon-carbon bond. In order to study the skeletal rearrangments that occur during the ring opening reactions of the cyclopentadienyl ligands, selectively isotopically labelled precursors will be prepared. A 1,2,3,-tri-t-butylcyclopenta- dienyl ligand has been prepared; advantage will be made of the incipient strain associated with the compound in order to make novel compounds. %%% By investigating in detail the mechanism of carbon-carbon bond making and breaking by transition metals, Dr. Russell P. Hughes of Dartmouth College hopes to achieve increased understanding of this reaction which is important to the petroleum catalyst industry. The results could be particularly relevant to the formation and control of carbon ring compounds.

在该奖项的支持下，达特茅斯学院化学系的Russell P.Hughes博士将继续研究过渡金属促进的碳-碳键的断裂和形成。将开展三个项目：乙烯基环丙烯重排中的开环；ETA-3-环丙烯基络合物的表征，包括它们的CO取代反应和旋转势垒；以及空间不稳定的环戊二烯配体的键断裂。后一种反应不是通过简单地将金属插入碳-碳键来进行的。为了研究环戊二烯基配体在开环反应中发生的骨架重排，将制备选择性同位素标记的前体。1，2，3-三叔丁基环戊二烯基配体已被制备，将利用该化合物的初始菌株来合成新的化合物。%通过详细研究过渡金属形成和断裂碳-碳键的机理，达特茅斯学院的Russell P.Hughes博士希望加深对这一反应的理解，这一反应对石油催化剂行业非常重要。这一结果可能对碳环化合物的形成和控制特别相关。