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

基本信息

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

项目摘要

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。无支持的 RE-TM 债券由于其高反应性而难以获得。它们是高极性的，或者更好的是最具极性的金属-金属键，因此代表了该研究领域的极端。 RE-TM 键的反应性及其键极性允许获得金属 RE-TM 簇。它们基于双金属配合物和金属间 RE-TM 化合物之间的化学键合。后者有多种应用，例如能源技术相关应用——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 债券和金属 RE-TM 簇领域的最新技术。在上一个（第一个）资助期内，已出版了六篇手稿，并提交了书籍章节。第二期拟资助的子项目如下： 1．能够与 RE 形成无支撑键的新型 TM 复合物部分能够与 RE 形成稳定的无支撑键的 TM 复合物部分的鉴定，对于此处计划的研究以及整个极性金属-金属键领域的进一步发展至关重要。因此，进一步的工作将基于第一期资助所取得的成果。2． RE-TM债券的反应性研究在第一期资助中，新型双茂金属已被制备出来。它们应该允许对 RE-TM 债券的反应性进行更集中的研究。此外，两次 TM 键合的二价 RE 的反应性也很有趣。 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支持用于催化应用通过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。这些研究将继续关于反应的系统化和新型簇的合成。此外，还计划在耐热且化学惰性的氮化物基体中支持 RE-TM 簇。如此形成的混合材料用作坚固的双金属非均相催化剂。 4. f-Element TM 多重键合 f-element 和 TM 之间的多重键合尚不清楚，但在某些方面很有希望。在过去 50 年中，单阴离子二齿 N 配体已成功用于稳定支持的多重键。我们建议合成N配体稳定的异双金属配合物，其中RE或U可以与TM形成多重键。