Ligand control for enhanced reactivity and functionality of silicon-based compounds and materials

配体控制可增强硅基化合物和材料的反应性和功能性

• 批准号: 411332998
• 负责人: Professor Dr. Lutz Greb
• 金额: --
• 依托单位: Anorganisch-Chemisches Institut
• 依托单位国家: 德国
• 项目类别: Independent Junior Research Groups
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/411332998?language=en
• 关键词: Ligand; control; enhanced; reactivity; functionality

This proposal establishes a ligand-oriented perspective for enhanced main group reactivity and functionality. Joint synthetic-theoretical efforts will answer fundamental questions and significantly broaden the possibilities of main group compounds in catalysis and material science.Conventional compounds of the p-block elements usually show classical reactivity and are absorbing light rather in the UV-spectral region. Developments during the last decades revealed that compounds with p-block elements in unusual states can mimic the reactivity of transition metals. Key for such behavior was most often the sub valency of the central element in these compounds. The ligand was merely attributed to kinetic or thermodynamic stabilization. In contrast, the leitmotif of this proposal is the enhancement of reactivity and functionality of p-block compounds in their conventional valency states but by strong ligand-element interactions. It deals with very electron-deficient, electron-rich or photo addressable substituents on group 14 elements, mainly silicon, for their application in catalysis and material science. 1) Understanding and tuning of the influence of electron-deficient catecholate substituents will lead to silicon Lewis acids ideally suited for small molecule binding and bond activation. Formation of the strongest Lewis acid known to date is aspired. Moreover, the redox-activity inherent in catecholates will be used for the oxidative generation of silylium ions and open-shell silicon materials with switchable magnet properties. 2) The strong influence of electron rich substituents will be exploited for the first experimental determination of planar silicon inversion and finally lead to the experimental realization of planar tetravalent silicon(IV). Moreover, those substituents render electron-rich, cationic compounds as suitable for valence tautomerism between unprecedented heteroatom substituted silylium ions and silylium ylidenes. Such species have high potential in very challenging bond activation reactions. 3) Photo addressable substituents will allow for the visible-light induced reductive formation of new silylenes and for “on-demand” excited state reactivity of stable tetrylenes. Dipyrrinato substituents will be used first as light-harvesting groups that subsequently stabilize the formed photoproducts. More importantly, such studies will be pioneering for reversible bond-activation with tetrylenes by photo-induced non-equilibrium conditions. It will furthermore introduce a new class of group 14 dyes and tetrylenes. All concepts in this proposal are supported by own, preliminary quantum chemical computations.

该建议建立了一个以配体为导向的视角，以增强主基团的反应性和功能。联合合成理论的努力将回答基本问题，并显著拓宽催化和材料科学中主要基团化合物的可能性。p区元素的传统化合物通常表现出经典的反应性，并且在紫外光谱区域吸收光。过去几十年的发展表明，含有p区元素的化合物在不寻常的状态下可以模拟过渡金属的反应性。这种行为的关键通常是这些化合物中中心元素的亚价。该配体仅归因于动力学或热力学稳定。相比之下，这一建议的主旨是通过强配元相互作用增强p-嵌段化合物在其常规价态下的反应性和功能。它处理14族元素（主要是硅）上的非常缺电子、富电子或光寻址取代基，用于催化和材料科学。1)了解和调整缺电子儿茶酚酸取代基的影响将导致硅路易斯酸非常适合小分子结合和键激活。形成了迄今为止已知的最强的路易斯酸。此外，儿茶酚酸盐固有的氧化还原活性将用于氧化生成硅离子和具有可切换磁铁性质的开壳硅材料。2)利用富电子取代基的强大影响，首次实验确定平面硅的反转，最终实现平面四价硅的实验实现（IV）。此外，这些取代基使得富含电子的阳离子化合物适合于前所未有的杂原子取代的硅离子和硅烷之间的价互变。这些物种在极具挑战性的键激活反应中具有很高的潜力。3)光寻址取代基将允许可见光诱导的新硅烯的还原形成和稳定的四烯的“按需”激发态反应性。Dipyrrinato取代基将首先用作光收集基团，随后稳定形成的光产物。更重要的是，这些研究将在光诱导非平衡条件下与四烯的可逆键激活方面具有开创性。此外，还将介绍一类新的14族染料和四乙烯。本提案中的所有概念都得到了自己的初步量子化学计算的支持。