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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.

ABSTRACT: The Zintl anion (Ge2 As2 )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 (Ge2 As2 )2- , the heterometallic cluster anion [Au6 (Ge3 As)(Ge2 As2 )3 ]3- is obtained as its salt [K(crypt-222)]3 [Au6 (Ge3 As)(Ge2 As2 )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 (Gex As4-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 (Ge3 As)3- unit besides three (Ge2 As2 )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 (Ge3 As)(Ge2 As2 )3 ]3- . Reactions of the heavier homologues (Tt2 Pn2 )2- (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1, but dimers of ternary nine-vertex clusters, {[AuTt5 Pn3 ]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 (Ge2 As2 )2- , according to the DFT calculations.

SUBMITTER: Pan F

PROVIDER: S-EPMC7540319 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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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.

Pan Fuxing F Guggolz Lukas L Weigend Florian F Dehnen Stefanie S

Angewandte Chemie (International ed. in English) 20200804 38

The Zintl anion (Ge2 As2 )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 (Ge2 As2 )2- , the heterometallic cluster anion [Au6 (Ge3 As)(Ge2 As2 )3 ]3- is obtained as its salt [K(crypt-2 ...[more]

PMID: 32648322

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Project description:A new algorithm called Automatic Johnson Cluster Generator (AJCG) is presented, which, as its name indicates, allows the definition of the desired Johnson polyhedron to subsequently carry out all the possible permutations between the atoms that form this polyhedron. This new algorithm allows the exhaustive study of the structures' potential energy surface (PES). In addition, the AJCG algorithm is helpful for the study of three-dimensional compounds such as boranes or Zintl clusters and their structural derivatives with two or more different atoms. The automatic filling of vertices is particularly useful in mixed compounds because of the possibility of taking into account all possible configurations in the structure. As a test system, we investigated the arachno-type E6M24- (E = Si, Ge, Sn; M = Sb, Bi) structure which has eight vertices and complies with Wade-Mingos rules. Initially, we defined a bipyramidal structure (10 vertices), and filled the vertices with the atoms in all possible configurations. Since the selected system has eight atoms, the two remaining vertices were filled with pseudo atoms to complete the structure. After re-optimizing the initial population generated with AJCG, a large number of isomers with energy below 10 kcal mol-1 are identified. These results show that the most stable isomers possess homonuclear M-M bonds, except Sn6Bi24-. Although the overall putative minima differ at the PBE0-D3 and DLPNO-CCSD(T) levels, they are always competitive minima. In addition to using high-precision methodologies to correctly study relative energies, applying solvent effects in highly charged systems becomes mandatory. The aromatic character of these studied systems was demonstrated qualitatively with two- and three-dimensional mapping and quantitatively by calculating the value of the z-component of the induced magnetic field at the cage center, including scalar and spin-orbit correction for relativistic effects. The compounds studied have a high degree of aromaticity, which allows us to establish that despite structural modifications (i.e., from closo to arachno), the aromaticity is preserved.

Dataset Information

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.

Publications

Atom Exchange Versus Reconstruction: (Ge<sub>x</sub> As<sub>4-x</sub> )<sup>x-</sup> (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au<sub>6</sub> (Ge<sub>3</sub> As)(Ge<sub>2</sub> As<sub>2</sub> )<sub>3</sub> ]<sup>3</sup>.

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