Lanthanoid Transition Metal Bonding - from Unsupported Metal-Metal Bonds to the Controlled Synthesis of Highly Aggregated Systems

镧系过渡金属键合——从无支撑金属-金属键到高度聚集系统的受控合成

• 批准号: 204294955
• 负责人: Professor Dr. Rhett Kempe
• 金额: --
• 依托单位: Arbeitsgruppe Anorganische Chemie II
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/204294955?language=en
• 关键词: Lanthanoid; Transition; Metal; Bonding; Unsupported; Lanthanoid; Transition; Metal; Bonding; Unsupported

Subject of the project are covalent bonds between Rare Earth Metals (RE) and Transition Metals (TM). Unsupported RE-TM bonds are difficult to access due to their high reactivity. They are highly polar or better the most polar metal-metal bonds and, thus, represent an extreme in that field of research. The reactivity of RE-TM bonds and their bond polarity allow the access to metallic RE-TM clusters. They lay in terms of chemical bonding between bimetallic complexes and the intermetallic RE-TM compounds. The latter have divers, for instance, energy technology relevant applications - high performance batteries and H2 storage materials. The state of the art in the fields of unsupported RE-TM bonds and metallic RE-TM clusters is dominated by our work since 2008. In the last (first) funding period, six manuscripts have been published and on book chapter has been submitted.The following subprojects are proposed for the second period of funding:1. Novel TM complex moieties able to form unsupported bonds to REThe identification of TM complex moieties, able to form stable unsupported bonds to RE, is essential for the further development of the research planned here and the field of polar metal-metal bonds in general. Further work is consequently based on results obtained in the first period of funding.2. Reactivity studies of RE-TM bondsIn the first period of funding, novel bismetallocenes have been prepared. They should allow a more focused study of the reactivity of RE-TM bonds. Furthermore, the reactivity of two times TM-bonded two-valent RE is of interest. 3. Generation of metallic RE-TM clusters via C-H bond activation and their supporting in nitride matrixes for catalytic applicationsThe synthesis of metallic SE-TM clusters via C-H activation has been one of the most productive subprojects of the first funding period. These investigations will be continued with regard to the systematization of the reactions and the synthesis of novel clusters. In addition, supporting of RE-TM clusters in thermally robust and chemically inert nitride matrixes is planned. The so formed hybrid materials are used as robust bimetallic heterogeneous catalysts. 4. f-Element TM multiple bondingMultiple bonding between f-elements and TM are not known but promising in a few regards. In the last 50 years, monoanionic bidentate N ligands have been successfully used to stabilize supported multiple bonds. We propose the synthesis of N ligand stabilized heterobimetallic complexes in which RE or U can form multiple bonds with TM.

该项目的主题是稀土金属（RE）和过渡金属（TM）之间的共价键。由于反应性的高反应性，不受支持的RE-TM键很难获得。它们是高度极性或更高的极性金属金属键，因此在该研究领域代表了极端。 RE-TM键的反应性及其键极性允许访问金属RE-TM簇。它们基于双金属复合物与金属间RE-TM化合物之间的化学键合。后者具有潜水员，例如能源技术相关的应用 - 高性能电池和H2存储材料。自2008年以来我们的工作主导了我们的工作中，无支撑的RE-TM债券和金属RE-TM簇领域的最新技术状况。在上一（第一个）资金期间，已经出版了六个手稿，并在书籍章节上提交了以下书籍。第二阶段的资金阶段提出了资金的第二阶段。新型的TM复合部分能够形成不支持的键以重新识别TM复杂部分的鉴定，能够形成稳定的无支撑键，这对于在此计划的进一步发展和一般的极性金属金属键的领域是至关重要的。因此，进一步的工作是基于在第一阶段的资金中获得的结果。2。 RE-TM键的反应性研究在第一阶段的资金阶段，已经准备好了新型的苯甲酸烯。它们应允许对RE-TM键的反应性进行更集中的研究。此外，两次TM键入的两次价值的反应性令人感兴趣。 3。通过C-H键激活生成金属RE-TM簇，及其在硝酸盐基质中用于催化应用的支持，通过C-H激活的金属SE-TM簇的合成一直是第一个资金期间最有生产力的亚标准之一。关于反应的系统化和新簇的合成，这些研究将继续进行。另外，计划在热稳定和化学惰性氮化物基质中支持RE-TM簇。 SO形成的杂种材料用作强大的双金属异质催化剂。 4。F-元素TM多键键合在F-元素和TM之间是不知道的，但在一些方面有希望。在过去的50年中，单位离子的双齿N配体已成功地用于稳定支持的多个键。我们提出了N配体稳定的异金属金属复合物的合成，其中RE或U可以与TM形成多个键。