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

该项目的主题是稀土金属（RE）和过渡金属（TM）之间的共价键。无支撑的RE-TM键由于其高反应性而难以接近。它们是高极性的，或者更好地是最极性的金属-金属键，因此代表了该研究领域的一个极端。RE-TM键的反应性和它们的键极性允许进入金属RE-TM簇。它们是稀土金属间化合物与稀土金属间化合物之间的化学键。后者具有多种应用，例如，能源技术相关应用-高性能电池和H2存储材料。自2008年以来，我们的工作主导了无支撑RE-TM键和金属RE-TM簇合物领域的最新技术。在上一个（第一个）资助期内，已经出版了六份手稿，并提交了一本书的章节。新的TM络合物部分能够形成无支撑键RE的TM络合物部分，能够形成稳定的无支撑键RE的鉴定，是必要的进一步发展的研究计划在这里和领域的极性金属-金属键一般。因此，今后的工作将以第一个供资期取得的成果为基础。RE-TM键的反应性研究在第一阶段的资金，新的bisobutenes已经准备好。它们应该允许更集中地研究RE-TM键的反应性。此外，两次TM键合的二价RE的反应性是感兴趣的。3.通过C-H键活化生成金属RE-TM簇及其在氮化物基质中的催化应用通过C-H活化合成金属SE-TM簇是第一个资助期最具成效的子项目之一。这些调查将继续与系统化的反应和合成新的集群。此外，计划在热稳定和化学惰性氮化物基质中支持RE-TM簇。如此形成的杂化材料用作稳健的非均相催化剂。4. f-元素TM多重键f-元素和TM之间的多重键尚不清楚，但在一些方面很有希望。在过去的50年里，单阴离子双齿N配体已被成功地用于稳定负载的多重键。我们提出了N配体稳定的杂环配合物的合成，其中RE或U可以与TM形成多重键。

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.