Atom Exchange Versus Reconstruction: (Ge(x) As(4-x) )(x-) (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au(6) (Ge(3) As)(Ge(2) As(2) )(3) ](3).
Atom Exchange Versus Reconstruction: (Ge(x) As(4-x) )(x-) (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au(6) (Ge(3) As)(Ge(2) As(2) )(3) ](3).
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DOI：
10.1002/anie.202008108
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发表时间：
2020-09-14
期刊：
影响因子：
--
通讯作者：
Dehnen S
中科院分区：
文献类型：
--
作者：
Pan F;Guggolz L;Weigend F;Dehnen S
Zintl 阴离子 (Ge2As2)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 [(PPh3)AuMe] 引入 (Ge2As2)2− 的 1,2-二氨基乙烷 (en) 溶液中后，获得异金属簇阴离子 [Au6(Ge3As)(Ge2As2)3]3− 及其盐 [K(crypt‐222)]3[Au6(Ge3As)(Ge2As2)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 (GexAs4−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除三个 (Ge2As2)2− 单元外还存在一个 (Ge3As)3− 单元，排除了除 [Au6(Ge3As)(Ge2As2)3]3− 之外的所有其他成分。较重的同系物 (Tt2Pn2)2− (Tt=Sn, Pb; Pn=Sb, Bi) 的反应不会产生与 1 中对应的簇，而是产生三元九顶点簇的二聚体，{[AuTt5Pn3]2}4− （在 2-4 中；Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb），因为底层根据 DFT 计算，包含较重原子的伪四面体单元不像 (Ge2As2)2− 那样容易发生所述交换反应。 超四面体簇[Au6(Ge3As)(Ge2As2)3]3−由[(PPh3)AuMe]和二元Zintl阴离子(Ge2As2)2−获得，它很容易在溶液中进行原位原子交换形成(GeAs3)−和(Ge3As)3−。后者需要形成产物，该产物包含相对于此类簇中的主族（半）金属原子而言最大数量的Au原子。
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 2–4; 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. The supertetrahedral cluster [Au6(Ge3As)(Ge2As2)3]3− is obtained from [(PPh3)AuMe] and the binary Zintl anion (Ge2As2)2−, which readily undergoes an in situ atom exchange in solution to form (GeAs3)− and (Ge3As)3−. The latter is required to form the product, which comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters.
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影响因子：
4.9
作者：
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