Gentner Thomas X, Evans Matthew J, Kennedy Alan R, Neale Sam E, McMullin Claire L, Coles Martyn P, Mulvey Robert E
Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.
School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington, New Zealand.
Chem Commun (Camb). 2022 Jan 27;58(9):1390-1393. doi: 10.1039/d1cc05379e.
Expanding knowledge of low valent aluminium chemistry, rubidium and caesium aluminyls are reported to complete the group 1 (Li-Cs) set of metal aluminyls. Both compounds crystallize as a contacted dimeric pair supported by M⋯π(arene) interactions with a pronounced twist between aluminyl units. Density functional theory calculations show symmetrical bonding between the M and Al atoms, with an Al centred lone-pair donating into vacant Rb and Cs orbitals. Interestingly, despite their structural similarity the Cs aluminyl enables C-H bond activation of benzene, but not the Rb aluminyl reflecting the importance of the alkali metal in these heterobimetallic systems.
随着对低价铝化学认识的不断扩展，据报道铷和铯铝化物完善了第1族（锂 - 铯）金属铝化物的体系。这两种化合物均以接触二聚体对的形式结晶，通过M⋯π(芳烃)相互作用得到支撑，且铝化物单元之间存在明显扭曲。密度泛函理论计算表明，M和Al原子之间存在对称键合，以Al为中心的孤对电子向铷和铯的空轨道提供电子。有趣的是，尽管它们结构相似，但铯铝化物能够实现苯的C - H键活化，而铷铝化物则不能，这反映了碱金属在这些异双金属体系中的重要性。
