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Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn₂Sb₅]³.

ABSTRACT: Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. Here we report the synthesis, experimental, and theoretical characterizations of four ternary clusters ([M₂(CO)₆Sn₂Sb₅]^3- (M = Cr, Mo), and [(MSn₂Sb₅)₂]^4-, (M = Cu, Ag)) in the process of capturing the hypho- [Sn₂Sb₅]^3- in ethylenediamine (en) solution. We show that the coordination of the binary anion to transition-metal ions or fragments provides additional stabilization due to the formation of locally σ-aromatic units, producing a spherical aromatic shielding region in the cages. While in the case of [Mo₂(CO)₆Sn₂Sb₅]^3- stabilization arises from locally σ-aromatic three-centre and five-centre two-electron bonds, aromatic islands in [(AgSn₂Sb₅)₂]^4- and [(CuSn₂Sb₅)₂]^4- render them globally antiaromatic. This work describes the coordination chemistry of the versatile building block [Sn₂Sb₅]^3-, thus providing conceptual advances in the field of metal-metal bonding in clusters.

SUBMITTER: Xu YH

PROVIDER: S-EPMC8298489 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn2Sb5]3.

Xu Yu-He YH Tkachenko Nikolay V NV Popov Ivan A IA Qiao Lei L Muñoz-Castro Alvaro A Boldyrev Alexander I AI Sun Zhong-Ming ZM

Nature communications 20210722 1

Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. Here we report the synthesis, experimental, and theoretical characterizations of four ternary clusters ([M2(CO)6Sn2Sb5]3- (M = Cr, Mo), and [(MSn2Sb5)2]4-, (M = Cu, Ag)) in the process of capturing the hypho- [Sn2 ...[more]

PMID: 34294702

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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

Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn₂Sb₅]³.

Publications

Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn<sub>2</sub>Sb<sub>5</sub>]<sup>3</sup>.

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