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.

在无机、生物无机和有机金属项目的支持下，达特茅斯学院化学系的拉塞尔·p·休斯博士将继续研究过渡金属促进碳-碳键的解理和形成。将进行三个项目：乙烯基环丙烯重排开环；-3-环丙烯配合物的表征，包括其CO取代反应和旋转势垒；以及空间不稳定环戊二烯配体的键裂解。后一种反应不是通过简单的金属插入碳-碳键来进行的。为了研究环戊二烯基配体开环反应中发生的骨架重排，将制备选择性同位素标记前体。制备了1,2,3，-三叔丁基环戊二烯基配体；将利用与该化合物相关的初始菌株以制造新的化合物。达特茅斯学院的拉塞尔·p·休斯博士希望通过详细研究过渡金属形成和破坏碳-碳键的机理，加深对这一反应的了解，这对石油催化剂工业非常重要。该结果可能与碳环化合物的形成和控制特别相关。