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RE-TM键由于其高反应性而难以获得。它们是高度极性的，或者说是最极性的金属-金属键，因此代表了该研究领域的一个极端。RE-TM键的反应性及其键极性允许获得金属RE-TM簇。它们在于双金属配合物和金属间RE-TM化合物之间的化学键。后者有多种用途，例如，与能源技术相关的应用——高性能电池和氢气储存材料。自2008年以来，我们的工作主导了无支撑RE-TM键和金属RE-TM团簇领域的最新技术。在最后（第一个）资助期间，已出版了六篇手稿，并提交了一本书章节。为第二供资期提议的分项目如下：能够与稀土形成稳定无负载键的TM络合物的鉴定，对于本研究的进一步发展以及整个极性金属-金属键研究领域都是至关重要的。因此，进一步的工作是根据第一个筹资期间取得的成果。RE-TM键的反应性研究在第一期资助中，制备了新型双金属茂物。它们应该允许对RE-TM键的反应性进行更集中的研究。此外，两倍tm键合的二价稀土的反应性值得关注。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有成效的子项目之一。关于反应的系统化和新簇的合成，这些研究将继续进行。此外，RE-TM簇在热稳定性和化学惰性氮化基体中的支持也在计划之中。所制备的杂化材料可用作坚固的双金属非均相催化剂。4. f-元素与TM之间的多重键合尚不清楚，但在一些方面很有希望。在过去的50年里，单阴离子双齿N配体已经成功地用于稳定负载的多键。我们建议合成N配体稳定的杂双金属配合物，其中稀土或铀可以与TM形成多个键。

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.