[Cd(Sn_(9))_(2)]^(6-) and[Cd(Ni@Sn_(9))_(2)]^(6-):Reactivity and coordination chemistry of empty and Ni-centered[Sn_(9)]^(4-) Zintl ions  

作　　者：Ya-Nan Yang Lei Qiao Zhong-Ming Sun 

机构地区：[1]State Key Laboratory of Elemento-Organic Chemistry,Tianjin Key Lab of Rare Earth Materials and Applications,School of Material Science and Engineering,Nankai University,Tianjin 300350,China

出　　处：《Chinese Chemical Letters》2023年第1期523-526,共4页中国化学快报（英文版）

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。

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.

关 键 词：Heterometallic complexes Sn cluster Zintl anions DFT calculation Electronic structure 

分 类 号：O62[理学—有机化学]