Lanthanides and Actinides in the +1 Oxidation State

第一氧化态的镧系元素和锕系元素

• 批准号: EP/X036626/1
• 负责人: Richard Layfield
• 金额: $ 111.93万
• 依托单位: University of Sussex
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FX036626%2F1
• 关键词: Lanthanides; Actinides; +1; Oxidation; State

The lanthanides and actinides, known collectively as the f-block elements, constitute approximately a quarter of the periodic table. The chemical and physical properties of these elements are indispensable to modern society. Lanthanides are at the heart of a huge variety of technological applications, ranging from medical imaging, computer HDDs and bulk magnets, to defence technology and optical materials. The actinides thorium, uranium and plutonium are used in nuclear fission reactors, a technology earmarked for growth as part of the UK's net-zero strategy.The chemistry and physics of lanthanide and actinide compounds depends strongly on the oxidation state of the metal. For the lanthanides, oxidation state +3 is ubiquitous whereas compounds containing these elements in oxidation states +2 and +4 are known in a limited number of cases. For the early actinides, oxidation states range from +3 up to +6 or +7, and the highly reactive oxidation state +2 has recently been observed. This project will focus on the synthesis and characterization of the first compounds containing the lanthanides and the early actinides (thorium-plutonium) in the elusive +1 or monovalent oxidation state.The PI's recent report of the first uranium(I) compound signposts a route to a family of monovalent lanthanide and actinide compounds. At the outset, we focus on monovalent lanthanides, aiming to synthesize a series of metallocene-like sandwich compounds and to determine the factors upon which the properties of these unusual compounds depends. In parallel, we will synthesize monovalent metallocenes of the early actinides thorium, uranium, neptunium and plutonium.A core goal of the project is to combine observations from synthetic and structural chemistry with detailed physical characterization and theoretical studies. This approach will provide quantitative insight into the electronic structure and chemical bonding of monovalent f-elements, including descriptions of the ionic and covalent contributions. The structure-property relationship will be used to design reactivity studies, with an emphasis on small-molecule activation using highly reducing monovalent f-elements. The electronic structure of monovalent lanthanides should be more diverse than for these elements in conventional oxidation states. As a result, contrasting reactivity for neighbouring lanthanides could occur, potentially requiring standard descriptions of f-element chemistry in terms of the lanthanide and actinide contractions to be revised.In addition, we will embed impact into the project through a new international collaboration with colleagues in Germany, through a programme of engagement activities aimed at inspiring the public with our science, and through the career development of the Sussex team members via participation in various training programmes relevant to the scientific objectives.

灯笼和actinides统称为F块元素，约占元素周期表的四分之一。这些元素的化学和物理特性对于现代社会来说是必不可少的。灯笼是各种技术应用的核心，从医学成像，计算机HDD和散装磁铁到国防技术和光学材料。 Actinides Thorium，铀和p-用于核裂变反应堆，该技术专门用于增长，作为英国零净策略的一部分。兰烷基和actacinide化合物的化学和物理学在很大程度上取决于金属的氧化状态。对于灯笼，氧化态+3无处不在，而在有限的情况下，氧化态中包含这些元素的化合物+2和+4是已知的。对于早期的actinides，氧化态范围从+3到+6或+7，并且最近观察到高反应性氧化态+2。该项目将重点介绍含有灯笼剂和早期actacinides（thor-plutonium）的第一个化合物的合成和表征，或者是单价氧化状态。对于一个单价灯笼和actacinide化合物的家族。首先，我们专注于单价灯笼，旨在合成一系列类似金属钙的三明治化合物，并确定这些异常化合物所依赖的特性所依赖的因素。同时，我们将合成早期actactinides thor，铀，海王星和plut的单价金属聚胶。该项目的核心目标是将合成和结构化学的观测结果与详细的物理表征和理论研究结合在一起。这种方法将提供对单价F元素的电子结构和化学键合的定量见解，包括对离子和共价贡献的描述。结构 - 培训关系将用于设计反应性研究，重点是使用高度还原的单价F元素进行小分子激活。对于传统氧化状态中的这些元素，单价灯笼的电子结构应更加多样化。结果，可能会发生相邻灯笼的反应性，可能需要修改F-元素化学的标准描述。在德国，通过一项旨在通过我们的科学来激发公众的参与活动计划，以及通过参与与科学目标相关的各种培训计划的苏塞克斯团队成员的职业发展。