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Hydrocarbon activation by f-block complexes

f-嵌段配合物活化烃

基本信息

批准号：
EP/H004823/1
负责人：
Polly Arnold
金额：
$ 189.7万
依托单位：
University of Edinburgh
依托单位国家：
英国
项目类别：
Fellowship
财政年份：
2009
资助国家：
英国
起止时间：
2009 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FH004823%2F1
关键词：
Hydrocarbon activation block complexes

项目摘要

Burning petrol and other hydrocarbons from fossil fuels is damaging to the environment and wasteful of resources that could otherwise be used to make substances that improve the quality of life. However, the strength of the carbon-hydrogen bond, coupled with the difficulties associated with selectively accessing a specific site on a particular molecule, means that highly reactive metal compounds are needed to catalyse such processes.A single C-H bond in methane, the simplest and most abundant hydrocarbon, is potentially the most financially important target for selective functionalisation, but the activation of C-H bonds in more complex hydrocarbons is also a highly desirable 'toolbox' component for scientists working in all areas of chemical synthesis. This selectivity will become increasingly more important as our palette of platform chemicals changes from fossil fuel-derived to biomass-derived in the coming years.Organometallic compounds of the lanthanides and actinides first gave a tantalising glimpse of their potential with the selective cleavage of one C-H bond in methane some 25 years ago, but the limitations of the supporting ligands precluded any further functionalisation step. Since then, a variety of C-H bond activation chemistry has been demonstrated at d- and f-block metal centres that has increased our fundamental understanding of this reaction, but not yet provided profitable applications. Recent advances in organometallic f-block chemistry (both in terms of academic breakthroughs, and characterisation methods), and the desire to find C-H activation catalysts not based on the rare and expensive platinum group metals, is now pushing f-block metals back to the forefront of C-H bond activation chemistry.We have made a variety of contributions to organometallic f-block chemistry that challenge traditional views of f-block structure and bonding, such as the isolation of f-block complexes with new polar metal-element bonds (J. Am. Chem. Soc. 2007), and the demonstration of unprecedented reactivity of the U=O oxo groups of the uranyl dication towards C-Si and N-Si bond cleavage (Nature, 2008).The proposed programme of work focuses on the selective activation and functionalisation of hydrocarbon C-H bonds, and builds on our recent successes and proof-of-concept results in functional organolanthanide and actinide chemistry. We have identified three mechanistically distinct types of C-H bond activation, and have combined them into one programme, to offer the highest chance of success. A fellowship offers the ideal opportunity for the PI to manage this intensive and internationally collaborative research programme and deliver new f-block catalysts for hydrocarbon activation.This work contributes to the Energy priority, by providing catalytic, atom-efficient, low-energy chemical routes to convert hydrocarbons from biomass or fossil fuels into high-value chemicals, so benefitting both industry and society.The fundamental understanding that comes from the reactivity and bonding studies of unusual f-block compounds improves our ability to handle nuclear materials and wastes, while the researchers on this project will gain actinide handling skills that are identified as a key shortage in the UK. Finally, the demonstration of important hydrocarbon chemistry by depleted uranium compounds would help to enhance the public image of uranium in our future nuclear age.

从化石燃料中燃烧汽油和其他碳氢化合物会破坏环境，浪费资源，而这些资源本来可以用来制造改善生活质量的物质。然而，碳-氢键的强度，加上与选择性地进入特定分子上的特定位点相关的困难，意味着需要高反应性的金属化合物来催化这样的过程。甲烷（最简单和最丰富的烃）中的单个C-H键可能是选择性官能化的最经济重要的目标，但是在更复杂的烃中C-H键的活化也是在化学合成的所有领域工作的科学家高度期望的“工具箱”组件。随着未来几年我们的平台化学品从化石燃料衍生到生物质衍生，这种选择性将变得越来越重要。大约25年前，镧系元素和锕系元素的有机化合物首次通过选择性裂解甲烷中的一个C-H键而展示了它们的潜力，但支持配体的限制排除了任何进一步的功能化步骤。从那时起，各种C-H键活化化学已被证明在d-和f-块金属中心，增加了我们对这个反应的基本理解，但尚未提供有利可图的应用。有机金属f-区化学的新进展（在学术突破和表征方法方面），以及希望找到不基于稀有和昂贵的铂族金属的C-H活化催化剂，我们对有机金属f-区化学做出了各种贡献，挑战了传统的f-区化学观点。嵌段结构和键合，例如具有新的极性金属-元素键的f-嵌段络合物的分离（J. Am. Soc. 2007），以及铀酰二价阳离子的U=O氧代基团对C-Si和N-Si键断裂的前所未有的反应性的证明（Nature，2008）。拟议的工作计划侧重于烃C-H键的选择性活化和官能化，并建立在我们最近的成功和功能有机镧系元素和锕系元素化学的概念验证结果的基础上。我们已经确定了三种不同类型的C-H键激活机制，并将它们结合到一个程序中，以提供最高的成功机会。该奖学金为PI提供了理想的机会来管理这一密集的国际合作研究计划，并提供用于碳氢化合物活化的新型f区催化剂。这项工作有助于能源优先事项，通过提供催化，原子效率，低能耗的化学路线，将生物质或化石燃料中的碳氢化合物转化为高价值的化学品，因此对工业和社会都有好处。来自不寻常的f区化合物的反应性和成键研究的基本理解提高了我们处理核材料和废物的能力，而该项目的研究人员将获得锕系元素处理技能，这被认为是英国的关键短缺。最后，用贫铀化合物展示碳氢化合物的重要化学性质将有助于提高铀在未来核时代的公众形象。