Low-coordinate Compounds of Main Group Elements and their application in the activation of H2, CO, CO2 and NH3

主族元素低配位化合物及其在H2、CO、CO2和NH3活化中的应用

• 批准号: 435224417
• 负责人: Dr. Alexander Hinz
• 金额: --
• 依托单位: Institut für Anorganische Chemie (aoc)
• 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/435224417?language=en
• 关键词: Low; coordinate; Compounds; Main; Group

The controllable transformation of small molecules such as H2, CO, CO2 and NH3 has been a relevant research area for both transition metal and main group chemists. To achieve this, in general the synthesis of particularly reactive compounds is necessary. For their stabilisation three methods have been employed: steric shielding, tuning of electronic properties by the substituents and the coordination of additional Lewis acids or bases. In previous projects we developed sterically encumbering monodentate monoanionic Subsituents for this purpose. Based on these substituents we propose the utilisation of monocoordinate atoms in molecules for the synthesis of reactive main group element compounds. Further development of sterically demanding substituents is an integral part of all three subprojects. The first project is focused on the chemistry of heavy tetrylenes. Halotetrylenes bearing bulky carbazolyl substituents will be studied with respect to halogen abstraction and reduction, thereby allowing access to building blocks of the general composition [R–E14]+/0/–. These offer various further options for derivatisation by both metathesis reactions and the stoichiometric reaction with small molecules, allowing systematic access to tetrylenes with tunable electronic properties. These tetrylenes could be used in the transformation of small molecules as well. The second projects is aimed at the investigation of a new class of multiple bonds. Heavy analogs of nitriles and isonitriles with heavy elements of group 14 are hitherto unknown, but they promise to possess interesting reactivity. For heavy nitrile analogs there is a balance of electronic influences that should enable reactivity between nitrene and nitride. In isonitrile analogs the group 14 element is monocoordinated; consequently there are various possible reaction pathways with small molecule substrates. Following the syntheses of achetypical multiple bond syntheses and a thorough analysis of bonding in them, their reactivity towards small molecules and metal complexes should be studied. The third project targets the synthesis of carbazolyl complexes in which Lewis acidity dominates the reactivity. Structural motifs such as monocoordinate earth alkaline and earth metal compounds should be generated, as they already should be strong Lewis acids that react with a variety of small molecules. Furthermore, corresponding hydride complexes could be obtained. Both the cationic and the hydride compounds are going to be studied initially in stoichiometric, then in catalytic transformations of relevant substrates in reactions such as hydrosilylations, hydroborations and hydrogenations.

小分子（例如H2，CO，CO2和NH3）的受控转化一直是过渡金属和主要组化学家的相关研究领域。为了实现这一目标，通常必须合成特别反应性化合物。对于它们的稳定剂，已经采用了三种方法：空间屏蔽，通过子接头对电子特性进行调整以及其他路易斯酸或碱的配位。在以前的项目中，我们为此目的开发了一个在空间上单位的单位离子定量。基于这些取代基，我们提出了分子中单组原子的利用，以合成反应性主元素化合物。进一步开发了苛刻的取代基是所有三个副投影的组成部分。第一个项目的重点是重型教学精益的化学反应。载有大量甲壳唑基取代基的Halotetrylenes将在卤素抽象和还原方面进行研究，从而允许进入一般组成的构件[R – E14]+/0/ - 。这些提供了各种进一步的选择，可以通过小分子进行元理解反应和化学计量反应进行衍生化，从而使具有可调电子特性的pretyylenes有系统地访问。这些治疗烯也可以用于小分子的转化。第二个项目旨在调查新的多个债券类。硝酸盐和具有第14组重元素的异构体的重型类似物被隐藏到未知，但它们承诺具有潜在的情感。对于重氮类似物，电子影响的平衡应该可以使硝酸盐和硝酸盐之间的反应性。在异构体类似物中，第14组元素是单重点的。因此，与小分子底物有各种可能的反应途径。遵循具有型成型多键合成的合成以及对它们中的键合的彻底分析，应研究它们对小分子和金属络合物的反应性。第三个项目靶向甲壳唑基络合物的合成，其中刘易斯酸度主导了反应性。结构基序，例如单重点的地球碱性和地球金属化合物，因为它们已经应该是强烈的路易斯酸，它们与各种小分子反应。此外，可以获得相应的氢化物复合物。阳离子和流体动力学化合物最初都将在化学计量学上进行研究，然后在相关底物的催化转化中，例如氢聚基因，液压和氢化。