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

一氧化碳是非常重要的工业原料，并且在费-托工艺中通过用氢气还原而广泛用于大规模生产烃和醇。将CO分子直接偶联在一起以形成较大的（CO）n单元的概念是吸引人的;然而，尽管费托反应历史悠久，但一氧化碳已被证明在温和条件下对这种选择性同系化具有显著的抗性。环的、芳香族的、含氧碳阴离子CnOn 2-（n= 3-6）原则上可以通过这样的路线获得，这可能为直接从CO合成复杂的有机分子提供新的策略。在两个铀中心之间。在拟议的研究中，我们将研究该反应的机理，生成一个催化系统，并在铀结合的δ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）络合物，使组装更大的单位（CO）n，并研究其他重要的小分子，如CO2，通过这个系统的激活。

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.