CYCLOOLIGOMERISATION OF CO AT U(III) CENTRES AND RELATED STUDIES

CO在U(III)中心的环齐聚及相关研究

• 批准号: EP/E004334/1
• 负责人: Jennifer Green
• 金额: $ 16.41万
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2006
• 资助国家: 英国
• 起止时间: 2006 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE004334%2F1
• 关键词: CYCLOOLIGOMERISATION; CO; III; CENTRES; RELATED

Carbon monoxide is a very important industrial feedstock, and is used extensively for the large scale production of hydrocarbons and alcohols via reduction with hydrogen in the Fischer-Tropsch process. The concept of directly coupling CO molecules together directly to form larger units of (CO)n is an appealing one; however, despite the long history of the Fischer-Tropsch reaction, carbon monoxide has proven remarkably resistant to such selective homologation under mild conditions. The cyclic, aromatic, oxocarbon anions CnOn2- (n= 3-6), in principle, are accessible by such a route, which may provide new strategies for the synthesis of complex organic molecules directly from CO. This proposal builds on our very recent discovery of a uranium(III) organometallic complex which will reductively cyclise CO under very mild conditions to from the deltate dianion, C3O3 2-, held between two uranium centres. In the proposed research, we will study the mechanism of this reaction, generate a system which is catalytic, and carry out reactions on the uranium-bound deltate unit to form larger organic rings (e.g. reductic acid- an important antioxidant). We will also modify the uranium(III) complex to allow the assembly of larger units of (CO)n, and investigate the activation of other important small molecules, e.g. CO2, by this system.

一氧化碳是一种非常重要的工业原料，广泛用于费托法中氢还原法大规模生产烃类和醇类。直接将CO分子偶联在一起直接形成更大单位的（CO）n是一个吸引人的概念；然而，尽管费托反应历史悠久，一氧化碳已被证明在温和条件下对这种选择性同源性具有显著的抵抗力。原则上，可以通过这种途径获得环状、芳香、氧碳阴离子CnOn2- (n= 3-6)，这可能为直接从CO合成复杂的有机分子提供新的策略。这一建议建立在我们最近发现的铀（III）有机金属配合物的基础上，该配合物可以在非常温和的条件下将CO还原环化，生成位于两个铀中心之间的三角离子c3o32 -。在拟进行的研究中，我们将研究该反应的机理，生成一个具有催化作用的体系，并在铀结合的三角洲单元上进行反应，形成更大的有机环（例如还原酸-一种重要的抗氧化剂）。我们还将修改铀（III）配合物，使其能够组装更大单位的（CO）n，并研究该系统对其他重要小分子（如CO2）的激活作用。