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。无载体的RE-TM键很难获得，因为它们具有很高的反应性。它们是高极性的，或者更好的是最极性的金属-金属键，因此，代表了该研究领域的极端。RE-Tm键的反应性和它们的键极性允许进入金属RE-Tm团簇。它们存在于双金属络合物和金属间稀土-TM化合物之间的化学键。后者有潜水器，例如，与能源技术相关的应用-高性能电池和储氢材料。自2008年以来，我们的工作主导了无载体RE-TM键和金属RE-TM团簇领域的最新进展。在上一个(第一个)资助期，已经出版了六篇手稿，并提交了一本书的章节。第二个资助期建议了以下子项目：1.能够与稀土形成稳定的无支撑键的新型TM络合物基团的鉴定，对于本研究计划的进一步发展和整个极性金属-金属键领域的进一步发展是至关重要的。因此，进一步的工作将以第一阶段筹资所取得的成果为基础。稀土-TM键的反应性研究在第一阶段的资助中，已经制备了新型的双茂金属化合物。它们应该能够更有针对性地研究RE-TM键的反应性。此外，两倍Tm键合的二价稀土的反应性也令人感兴趣。3.通过C-H键活化生成金属RE-TM簇合物及其在氮化物基质中的支持用于催化应用通过C-H活化合成金属SE-TM簇合物一直是第一个供资期间最有成效的次级项目之一。这些研究将在反应的系统化和新型簇合物的合成方面继续进行。此外，还计划在耐热和化学惰性氮化物基质中支持RE-TM团簇。这样形成的杂化材料被用作坚固的双金属多相催化剂。4.f元素TM多重结合f元素与TM之间的多重结合尚不为人所知，但在某些方面很有希望。在过去的50年里，单阴离子双齿N配体被成功地用于稳定支撑的多键。我们建议合成N配体稳定的稀土或铀与Tm形成多键的异双金属配合物。

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.