Frustrated Lewis-Pairs with Silicon, Germanium and Tin as Lewis-acidic Functions

受挫路易斯对与硅、锗和锡作为路易斯酸性官能团

• 批准号: 320753677
• 负责人: Professor Dr. Norbert W. Mitzel
• 金额: --
• 依托单位: Arbeitsgruppe Anorganische Chemie und Strukturchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/320753677?language=en
• 关键词: Frustrated; Lewis; Pairs; Silicon; Germanium

The concept of frustrated Lewis acid base pairs (FLP) is based on the interaction between Lewis acids and bases, which are prevented from the formation of a classical adduct. The resulting unquenched reaction potential can be used to bind small molecules, cleave or activate them, e.g. for the heterolytic cleavage of hydrogen or for the activation of carbon dioxide and other greenhouse gases. In this way novel reactions and catalytic processes have become possible. Most of the known FLP chemistry is based on the elements boron and phosphorus, i.e. boranes and phosphanes as acids and bases. Other elements [acids: Al, Zn, P (V), Si+, bases: N, O] are much less explored. With the presentation of a first uncharged intramolecular silicon-phosphorus FLP, (C2F5)3SiCH2P(t-Bu)2, we were recently able to apply our long-standing expertise in the field of geminal donor-acceptor compounds successfully to the modern developments of FLP chemistry. The molecular chemistry of silicon is easily accessible because of its immense industrial importance; we now want to make use of this advantage for FLP chemistry.For this purpose, this project aims at generating novel intramolecular FLP systems of the type (RF)3SiCH2P(R)2, with RF representing electronegative (e. g. fluorinated) alkyl or aryl groups (z. B. C6F5, C5NF4, etc.) and R representing alkyl or amine functions (t-Bu, CH(SiMe3)2, NR'2, etc.). The length and type of the chain between the Si and P atoms will be varied. In addition to silicon germanium and tin will be used to offer softer binding partners in terms of the HSAB concept for the activation of small molecules that are thus bound more weakly and hence in terms of catalytic processes more easily removable. The concept to develop neutral Si-FLP systems will be transferred in a parallel subproject to intermolecular systems with separate acid and base molecules. The acids are compounds such as (RF)4Si, and the bases also include super basic systems such as phosphatranes. The resulting FLP systems will be tested for their activity of binding, activating small molecules and for their catalytic ability (e.g. hydrogenation of unsaturated substrates). Experiments with para-hydrogen will contribute the mechanistic insights. Advanced structural investigations include gas phase electron diffraction measurements for free molecule geometries and experimental charge density studies to shed more light on the bonding situation in more detail.

沮丧的刘易斯酸碱对（FLP）的概念是基于路易斯酸与碱之间的相互作用，这些相互作用阻止了经典加合物的形成。所得的未抑制反应电位可用于结合小分子，裂解或激活它们，例如用于氢的杂裂或激活二氧化碳和其他温室气体的激活。这样，新颖的反应和催化过程就变得可能成为可能。大多数已知的FLP化学基于硼和磷的元素，即硼烷和磷酸化作为酸和碱。其他元素[酸：al，zn，p（v），si+，bases：n，o]的探索少得多。随着第一个未充电的分子内硅 - 磷FLP（C2F5）3SICH2P（T-BU）2的介绍，我们最近能够将我们的长期专业知识应用于Geminal供体 - 受体化合物领域，成功地将其成功地用于FLP化学现代发展的现代发展。由于其巨大的工业重要性，很容易获得硅的分子化学。我们现在想利用这一优势进行FLP化学。为此，该项目旨在生成新型的分子内FLP系统（RF）3SICH2P（r）2，RF代表电负性（例如fluorationed）烷基或芳基烷基或芳基类（z。B.C6f5，C5NF4等），或代表B. C5NF4等（TES），或者代表Alkyyl或Ankyl，theyl或RANKYL或ANKYL或ANKYL ANKYL或ANKINE ANKYL或AIMINES ANKYL或AIMINE CH（Sime3）2，NR'2等）。 Si和P原子之间的链的长度和类型将变化。除了硅锗和锡外，还将使用HSAB概念来提供更柔和的结合伙伴，以激活小分子，因此更弱地结合了小分子，因此在催化过程方面更容易移动。开发中性Si-FLP系统的概念将以平行的亚概器传输到具有单独的酸和碱基分子的分子间系统。酸是（RF）4SI等化合物，碱还包括超碱性系统，例如磷酸丙烷。所得的FLP系统将测试其结合，激活小分子及其催化能力的活性（例如，不饱和底物的氢化）。使用Para-Hydrogen的实验将有助于机械见解。先进的结构研究包括自由分子几何形状的气相电子衍射测量和实验电荷密度研究，以更详细地阐明粘结状况。