Gold-2-Go

黄金-2-Go

• 批准号: 429630817
• 负责人: Professorin Dr. Katja Heinze
• 金额: --
• 依托单位: Department Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2019
• 资助国家: 德国
• 起止时间: 2018-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/429630817?language=en
• 关键词: Gold; Go

The preparation of isolable mononuclear gold(II) complexes is apart from very few examples poorly developed. Spectroscopic and chemical properties of mononuclear gold(II) complexes are essentially unknown. Consequently, this project targets true mononuclear gold(II) complexes. Gold(II) complexes with idealized square-planar and T-shaped coordination geometry will be kinetically stabilized by using tetradentate macrocyclic ligands or tridentate sterically demanding chelate ligands which shall enable spectroscopic, magnetic and structural characterization. The “true” electronic nature (metal vs. ligand centered radical) will be elucidated. Spectroscopically confirmed gold(II) complexes will be studied by structural analyses with respect to expected first and second order Jahn-Teller distortions. The reactivity (dimerization, disproportionation, redox reactions, radical reactions with substrates) of this underdeveloped complex class will be systematically probed for the first time. Specifically, gold(II) complexes with coordination numbers three and four are targeted. Dimerization via Au-Au sigma bonds will be blocked by four ligand donor atoms in the xy plane in the former case and by steric protection of the free coordination site in the second case. Computer-aided screening of macrocylic and tridentate ligands will be performed using quantum chemical methods. The electronic structure of experimentally accessible gold(II) complexes will be verified employing advanced quantum chemical techniques using large basis sets. The project will lay the foundation to exploit the potential of gold(II) complexes in catalysis, redox catalysis and possibly photoredox catalysis.

可分离的单核金（II）配合物的制备除了极少数的例子外，发展得很差。单核金（II）配合物的光谱和化学性质基本上是未知的。因此，该项目的目标是真正的单核金（II）配合物。金（II）配合物与理想的正方形平面和T形的协调几何形状将动力学稳定，通过使用四齿大环配体或三齿空间要求螯合配体，这将使光谱，磁性和结构表征。“真正的”电子性质（金属与配体中心的自由基）将被阐明。光谱确认的金（II）配合物将通过结构分析进行研究，相对于预期的第一和第二阶Jahn-Teller扭曲。反应性（二聚，反式异构化，氧化还原反应，与底物的自由基反应），这欠发达的复杂类将首次系统地探讨。具体而言，目标是具有配位数3和4的金（II）络合物。在前一种情况下，通过Au-Au σ键的二聚化将被xy平面中的四个配体供体原子阻断，而在第二种情况下，通过自由配位位点的空间保护阻断。将使用量子化学方法进行大环和三齿配体的计算机辅助筛选。实验上可访问的金（II）配合物的电子结构将采用先进的量子化学技术，使用大基组进行验证。该项目将为开发金（II）配合物在催化、氧化还原催化和可能的光氧化还原催化方面的潜力奠定基础。