Gold-2-Go

可分离的单核金（II）配合物的制备，除了极少数的例子外，还欠发达。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。具有理想的方形平面和t形配位几何的金（II）配合物将通过使用四齿大环配体或三齿立体要求的螯合配体进行动力学稳定，这将使光谱，磁性和结构表征成为可能。“真正的”电子性质（金属与配体中心自由基）将被阐明。光谱确认的金（II）配合物将通过结构分析来研究预期的一阶和二阶扬-泰勒扭曲。这类未开发的配合物的反应性（二聚化、歧化、氧化还原反应、与底物的自由基反应）将首次被系统地探讨。具体来说，目标是配位数为3和4的金（II）配合物。在前一种情况下，通过Au-Au - sigma键的二聚化将被xy平面上的四个配体供体原子所阻止，而在第二种情况下，则被自由配位位的空间保护所阻止。计算机辅助筛选大环和三叉配体将使用量子化学方法进行。实验可获得的金（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集进行验证。该项目将为开发金（II）配合物在催化、氧化还原催化以及可能的光氧化还原催化方面的潜力奠定基础。

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.