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

用于金属基催化的新型配体体系：合成、筛选和理论研究

• 批准号: EP/H031855/1
• 负责人: Carl Redshaw
• 金额: $ 6.54万
• 依托单位: University of East Anglia
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FH031855%2F1
• 关键词: New; ligand; systems; metal; based

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.

目前，远东地区的石化工业有了很大的增长。中国石化行业尤其如此。因此，目前在世界的这一地区，学术界对这一领域也有很大的兴趣，各种团体积极参与开发新的催化系统。这与英国的情况形成鲜明对比，英国的情况已经停滞了一段时间，大部分行业转移到欧洲大陆或美国，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，这反映在道尔顿交易即将在今年晚些时候出版烯烃聚合的特刊。正是在这种背景下，我们感到很好地保持了英国在烯烃聚合（和开环聚合）新催化剂开发方面的学术兴趣。我们与孙教授（北京）和大和教授（佐贺）的研究小组正在进行催化剂开发的实验研究，并由大坂的加塞小组进行理论研究。中国大陆（长春）、香港（城市大学和香港科技大学）和日本（熊本）的其他研究小组现在也热衷于加入该项目。一个相关的化学领域是利用杯芳烃组装体作为有机催化（和预硅氧烷聚合催化）的纳米罐。这包括通过半导体量子点吸收光子来产生红色/氧化电位。杯芳烃将紧密结合在QD的表面附近。小的有机“客人”分子将进入杯芳烃腔并被转化。与“直接”还原相比，通过反应物在杯芳烃上结合的熵收益，活化能（电化学还原电势）将降低。该项目将带来更多的专业知识，从PI自己的机构，与结果的指导下，在大坂进行建模。最后，肽杯芳烃框架将用于模拟二级相互作用中发现的所有铁氢化酶的活性位点。在大坂进行的计算表明，杯[5]芳烃平台最适合提供必要的铁-铁分离，合成工作将在大坂的理论研究指导下在UEA进行。