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Atom Exchange Versus Reconstruction: (Gex As4-x )x- (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au6 (Ge3 As)(Ge2 As2 )3 ]3.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-07-09 , DOI: 10.1002/anie.202008108
Fuxing Pan 1 , Lukas Guggolz 1 , Florian Weigend 1 , Stefanie Dehnen 1
Affiliation  

The Zintl anion (Ge2As2)2− represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh3)AuMe] into the 1,2‐diaminoethane (en) solution of (Ge2As2)2−, the heterometallic cluster anion [Au6(Ge3As)(Ge2As2)3]3− is obtained as its salt [K(crypt‐222)]3[Au6(Ge3As)(Ge2As2)3]⋅en⋅2 tol (1). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non‐bonding) octahedron of six Au atoms that is face‐capped by four (GexAs4−x)x (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge3As)3− unit besides three (Ge2As2)2− units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au6(Ge3As)(Ge2As2)3]3−. Reactions of the heavier homologues (Tt2Pn2)2− (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1, but dimers of ternary nine‐vertex clusters, {[AuTt5Pn3]2}4− (in 24; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo‐tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge2As2)2−, according to the DFT calculations.

中文翻译:

原子交换与重建:(Gex As4-x )x- (x=2, 3) 作为超四面体 Zintl 簇的构建块 [Au6 (Ge3 As)(Ge2 As2 )3 ]3。

Zintl 阴离子 (Ge 2 As 2 ) 2−代表黄砷的同构和等电子二元对应物,但迄今为止尚未进行相同强度的研究。将[(PPh 3 )AuMe]引入(Ge 2 As 2 ) 2−的1,2-二氨基乙烷(en)溶液中后,异金属簇阴离子[Au 6 (Ge 3 As)(Ge 2 As 2 ) 3 ] 3−以其盐形式获得 [K(crypt‐222)] 3 [Au 6 (Ge 3 As)(Ge 2 As 2 ) 3 ]⋅en⋅2 tol ( 1 )。该阴离子代表了超多面体 Zintl 簇的罕见例子,并且相对于此类簇中的主族(半)金属原子,它包含最多数量的 Au 原子。整体超四面体结构基于六个金原子的(非键合)八面体,其面由四个 (Ge x As 4− x ) x ( x =2, 3) 单元覆盖。Au原子以矩形方式与四个主族原子结合,从而将四个单元结合在一起形成这种前所未有的结构。通过详细的量子化学 (DFT) 计算验证了溶液中交换反应导致的除三个 (Ge 2 As 2 ) 2− 单元存在一个( Ge 3 As) 3− 单元,排除除[Au 6 (Ge 3 As)(Ge 2 As 2 ) 3 ] 3−。较重的同系物 (Tt 2 Pn 2 ) 2− (Tt=Sn, Pb; Pn=Sb, Bi) 的反应没有产生与1中对应的簇,而是三元九顶点簇的二聚体,{[AuTt 5 Pn 3 ] 2 } 4−(在24中;Tt/Pn=Sn/Sb、Sn/Bi、Pb/Sb),因为包含较重原子的基础四面体单元不容易发生所述交换反应根据DFT计算为(Ge 2 As 2 ) 2− 。
更新日期:2020-09-08
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