Catalytic ways to new inorganic polymers: development of transition metal catalysts for highly selective dehydropolymerisation of amine boranes

新型无机聚合物的催化方法：开发用于胺硼烷高选择性脱氢聚合的过渡金属催化剂

• 批准号: 419924354
• 负责人: Professor Dr. Torsten Beweries
• 金额: --
• 依托单位: Leibniz-Institut für Katalyse e. V. an der Universität Rostock (LIKAT)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/419924354?language=en
• 关键词: Catalytic; ways; new; inorganic; polymers

The field of so-called inorganic polymers has seen significant advances in recent years. Poly(aminoborane)s as inorganic analogues of ubiquitous polyolefins represent examples for compounds of this type, possessing a polymer main chain that exclusively contains boron and nitrogen. These structures are of fundamental and application-oriented interest in the context of BN/CC isosterism and as pre-ceramics for new B-N containing materials. Modification of the amine borane precursor itself, the poly(aminoborane), or the reactions conditions used for the synthesis of heterogeneous materials (i.e., temperature, atmosphere, metal dopants) could open new avenues in the chemistry of main group materials, including applications in heterogeneous catalysis. Within the framework of this project, the knowledge gained in the previous project on the catalytic dehydropolymerisation of methylamine-borane is to be extended to new catalysts based on group 9 metals. Previous investigations showed that mainly rhodium complexes as well as complexes with pincer ligands catalyse this reaction with high selectivity for the desired polymer. In the investigations now proposed, this approach is to be systematically pursued further and extended to include the use of pincer ligands with a modifiable secondary coordination sphere for metal-ligand cooperative binding, activation, dehydrogenation, and coupling of amine boranes. We will furthermore evaluate possibilities to replace phosphine-based ligands. The presented project will contribute to the mechanistic understanding of the reaction as well as to the development of new catalysts for the selective dehydropolymerisation of primary amine boranes. Furthermore, the possibility of synthesising poly(aminoboranes) on a large scale for use as precursors for new, modifiable B-N materials will be investigated.

近年来，所谓的无机聚合物领域取得了重大进展。作为普遍存在的聚烯烃的无机类似物的聚(氨基硼烷)代表了此类化合物的例子，其聚合物主链仅包含硼和氮。这些结构在 BN/CC 电子等排背景下具有基础性和应用导向性，并且可作为新型含 B-N 材料的陶瓷前体。 胺硼烷前体本身、聚（氨基硼烷）或用于合成异质材料的反应条件（即温度、气氛、金属掺杂剂）的改性可以在主族材料的化学中开辟新的途径，包括在多相催化。在该项目的框架内，之前在甲胺-硼烷催化脱氢聚合项目中获得的知识将扩展到基于第9族金属的新型催化剂。先前的研究表明，主要是铑配合物以及具有钳配体的配合物能够以高选择性催化该反应，生成所需的聚合物。在现在提出的研究中，这种方法将得到进一步系统地探索和扩展，包括使用具有可修饰的二级配位球的钳配体来进行金属-配体的协同结合、活化、脱氢和胺硼烷的偶联。我们还将进一步评估替代膦基配体的可能性。所提出的项目将有助于对反应机理的理解以及伯胺硼烷选择性脱氢聚合的新型催化剂的开发。此外，还将研究大规模合成聚（氨基硼烷）作为新型可改性 B-N 材料前体的可能性。