{[CuSn5 Sb3 ](2-) }2 : A Dimer of Inhomogeneous Superatoms.
{[CuSn5 Sb3 ](2-) }2 : A Dimer of Inhomogeneous Superatoms.
复制标题
{[CuSn5 Sb3 ](2-) }2 : 不均匀超原子的二聚体
DOI：
10.1002/anie.201603455
复制
发表时间：
2016
影响因子：
--
通讯作者：
S. Dehnen
中科院分区：
文献类型：
--
作者：
R.J. Wilson;L. Broeckaert;F. Spitzer;F. Weigend;S. Dehnen
二元锌离子(Sn2Sb2)2−在乙二胺或二甲基甲酰胺中与二酮亚胺配合物[Lcu(β)](L=NaCnAc=[(N(C6H3iPr2-2，6)C(Me))2CH]−)反应生成三元簇合物{[CuSn5Sb3]2−}2(1)作为其[K(Crypt-222)]+盐。1的化学式得到能量色散X射线光谱分析(EDX)和量子化学计算的支持。二聚体的每个单体部分代表一个三金属的“[CuSn5Sb3]2−”团簇，其结构位于一个三棱柱和一个带帽的正方形反棱镜之间。量子化学研究表明，Sb原子的存在，特别是铜原子在团簇骨架中的存在，使单体单元的行为像一个不均匀的超原子，显然倾向于二聚化，从而产生相对较短的但几乎没有成键的铜⋅⋅⋅-铜距离。
Reaction of the binary Zintl anion (Sn2Sb2)2−with the β‐diketiminato complex [LCu(NCMe)] (L=nacnac=[(N(C6H3iPr2‐2,6)C(Me))2CH]−) in ethylenediamine or DMF affords the ternary cluster dimer {[CuSn5Sb3]2−}2(1) as its [K(crypt‐222)]+salt. The chemical formulation of1is supported by energy‐dispersive X‐ray spectroscopy (EDX) and quantum chemical calculations. Each monomeric part of the dimer represents a trimetallic “[CuSn5Sb3]2−” cluster, with an architecture in between a tricapped trigonal prism and a capped square antiprism. As shown by quantum chemical investigations, the presence of Sb atoms and, in particular, of Cu atoms in the cluster skeleton makes the monomeric unit behave like an inhomogeneous superatom, which clearly prefers to dimerize, thereby producing a relatively short, yet virtually non‐bonding Cu⋅⋅⋅Cu distance.