[Cd(Sn9)2]6- and [Cd(Ni@Sn9)2]6-: Reactivity and coordination chemistry of empty and Ni-centered [Sn9]4- Zintl ions

To investigate the reactivity of homoatomic clusters [E-9](4-) (E = Si-Pb) and intermetalloid clusters [M@E-9](q-), the reactions of the Zintl anions [Sn-9](4-) and [Ni@Sn-9](4-) with the CdMes(2) (Mes = Mesitylene) in the presence of 2.2.2-crypt were carried out. Two new compounds [K(2.2.2-crypt)](6)[(Sn-9)Cd(Sn-9)] center dot en (1) and [K(2.2.2-crypt)](6)[(Ni @Sn-9)Cd(Ni @Sn-9)] center dot en (2) were afforded. Both 1 and 2 were characterized by single-crystal X-ray diffraction, energy dispersive X-ray (EDX), and electrospray ionization mass spectrometry (ESI-MS), and can be viewed as two [Sn-9](4-) or [Ni@Sn-9](4-) subunits bridged by Cd ion in an eta(3):eta(3) coordination mode. Quantum chemical calculations reveal the relationships between the geometries and electronic structures of clusters 2a , [Ni3Ge18](4-) and [Cu-4@Sn-18](4-). Further electron localization technique (AdNDP method) was performed to explain chemical bonding patterns of 1a . (c) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

In this study, the reactivity of homoatomic clusters [E-9](4-) (E = Si-Pb) and intermetalloid clusters [M@E-9](q-) was investigated. Two new compounds were synthesized and characterized using various analytical techniques. Quantum chemical calculations were conducted to analyze the relationships between the geometries and electronic structures of different clusters.