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

目前，远东地区的石油化学工业有很大的增长。中国石化行业尤其如此。因此，目前世界上该地区在这一领域也有很大的学术兴趣，各种团体积极参与新催化系统的开发。这与英国的情况形成了鲜明对比，英国的情况已经停滞了一段时间，许多行业转移到了欧洲大陆或美国，这对英国学术界造成了不可避免的负面连锁反应。然而，有趣的是，现在出现了复苏的迹象，这反映在道尔顿交易即将在今年晚些时候出版一期关于烯烃聚合的特刊。正是在这种背景下，我们感到有条件保持英国在开发用于烯烃聚合(和开环聚合)的新催化剂方面的学术兴趣。我们正在与孙教授(北京)和Yamato(佐贺)一起进行催化剂开发的实验研究，并辅之以大阪Kasai小组进行的理论研究。中国大陆的中国(长春)、香港(城市大学和科大)和日本(熊本)的其他团体现在都热衷于加入这项计划。一个相关的化学领域是利用杯芳烃组装作为有机催化的纳米粒子(可能也包括聚合催化)。这包括通过半导体量子点对光子的吸收来产生红/牛势。杯芳烃将紧密结合在量子点的表面。小的有机‘客体’分子将进入杯芳烃空腔并被转化。与直接还原相比，活化能(电化学还原电位)将因反应物在杯芳烃上的结合而降低。这个项目将引入来自PIS自身机构的更多专业知识，结果由在大阪进行的建模指导。最后，将使用多肽脂肪芳烃框架来模拟在所有铁氢酶活性部位发现的二级相互作用。在大阪进行的计算表明，杯[5]芳烃平台最适合提供必要的铁-铁分离，UEA将在大阪的理论研究指导下进行合成工作。

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.