摘要
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))]·en(1)and[K(2.2.2-crypt)]_(6)[(Ni@Sn_(9))Cd(Ni@Sn_(9))]·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 η^(3):η^(3) coordination mode.Quantum chemical calculations reveal the relationships between the geometries and electronic structures of clusters 2a,[Ni_(3)Ge_(18)]^(4-)and[Cu_(4)@Sn_(18)]^(4-).Further electron localization technique(Ad NDP method)was performed to explain chemical bonding patterns of 1a.
基金
supported by the National Natural Science Foundation of China(Nos.92161102 and 21971118)
the Natural Science Foundation of Tianjin City(Nos.20JCYBJC01560 and B2021202077)to Z.-M.Sun。
