Ríos Pablo, See Matthew S, Handford Rex C, Cooper Jason K, Don Tilley T
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica, Centro de Innovación en Química Avanzada (ORFEO-CINQA), CSIC and Universidad de Sevilla, 41092, Sevilla, Spain.
Department of Chemistry, University of California, Berkeley, USA.
Angew Chem Int Ed Engl. 2023 Nov 6;62(45):e202310307. doi: 10.1002/anie.202310307. Epub 2023 Sep 27.
Reactions of a dicopper(I) tert-butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ-acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single-crystal X-ray diffraction. These compounds possess an unusual μ -η :η :η :η coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal-metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne-containing clusters.
二叔丁氧基铜（I）配合物与带有硼基或硅基封端基团的炔烃反应，生成了前所未有的四铜（I）μ-乙炔化物/二炔配合物，通过核磁共振、紫外/可见光谱、质谱和单晶X射线衍射对其进行了表征。这些化合物对于桥连有机片段具有不寻常的μ -η :η :η :η配位模式，这是由所使用配体的刚性和双核性质所强制形成的。因此，中心π体系保持不受干扰，可用于后续的反应性和修饰。通过添加第五个铜原子得到五铜乙炔化物配合物，这一点得到了证实。这项工作可能提供一种新方法，通过该方法可以在乙炔化物和二炔基团向各种底物的转化中利用金属-金属协同作用，或者作为可控合成含铜（I）炔烃簇的起点。
