New ligand systems for metal-based catalysis: Synthesis, screening and theoretical studies

目前远东地区的石化工业有相当大的增长。中国石化行业尤其如此。因此，目前世界上该地区对该领域也有很大的学术兴趣，各种团体积极参与新的催化系统的开发。这与英国的情况形成鲜明对比，英国已经停滞了一段时间，大部分行业都转移到了欧洲大陆或美国，这对英国学术界产生了不可避免的负面影响。然而，有趣的是，现在有复苏的迹象，反映在道尔顿交易将在今年晚些时候出版一个关于烯烃聚合的特刊。正是在这样的背景下，我们觉得很有必要保持英国在烯烃聚合（和开环聚合）新催化剂开发方面的学术兴趣。我们正在与孙教授（北京）和大和教授（佐贺）的团队一起进行催化剂开发的实验研究，辅以大阪Kasai团队进行的理论研究。化学的一个相关领域是利用杯芳烃组件作为纳米点进行有机催化（也可能是聚合催化）。这包括通过半导体量子点吸收光子产生红/牛电位。杯芳烃将被绑定在量子点表面附近。小的有机“客人”分子将进入杯芳烃腔并进行转化。活化能（电化学还原电位）与“直接”还原相比，通过杯芳烃与反应物结合的熵利润而降低。该项目将从PIs自己的机构引入更多的专业知识，其结果将以在大阪进行的建模为指导。最后，肽链芳烃框架将用于模拟在所有铁氢化酶活性位点发现的二级相互作用。在大阪进行的计算表明，杯状[5]芳烃平台最适合提供所需的铁-铁分离，合成工作将在东英吉利大学进行，由大阪的理论研究指导。

There is currently substantial growth in the petrochemical industry in the Far East. This is particularly the case for the Chinese Petrochemical Industry. As a consequence, there is also currently a great deal of academic interest in the field in that part of the world, with various groups actively engaged in the development of new catalytic systems. This is in stark contrast to the situation in the UK, which has been stagnent for some time, with much of the industry moving to mainland Europe or the States, with an inevitable negative knock on effect for UK academia. Interestingly however, there are now signs of a recovery, reflected in the fact that Dalton Transactions are about to publish a special issue later this year on olefin polymerisation. It is against this background that we feel well-placed to maintain the UKs academic interest in the development of new catalysts for olefin polymerisation (and ring opening polymerisations). Our experimental studies on catalyst development are on-going with the groups of Profs Sun (Beijing) and Yamato (Saga), complemented by the theoretical studies conducted by the Kasai group in Osaka. Other groups in mainland China (Changchun), Hong Kong (City U and HKUST) and Japan (Kumamoto) are now keen to join the project.A related area of chemistry is to utilise calixarene assemblies as nanopots for organic catalysis (and prehaps also polymerisation catalysis). This includes generation of a red/ox potential by absorption of photons by semiconductor Quantum Dots. Calixarenes will be bound in close proximity to the QDs' surface. Small organic 'guest'-molecules will enter the calixarene cavity and be transformed. The activation energy (electrochemical reduction potential) will be reduced as compared with 'direct' reduction by entropic profit of the binding of the reactants at the calixarene. This project will bring on board added expertise from the PIs own institution, with results guided by modelling performed in Osaka.Finally, peptidocalixarene frameworks will be used to mimic the secondary interactions found in the active site of all iron hydrogenase. Calculations performed in Osaka suggets that a calix[5]arene platform is best suited to provide the requisite iron - iron separation, and synthetic work will be conducted at UEA, guided by the theoretical studies in Osaka.