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• W2793642292 abstract "Characterization of the tetrahedral Au20 structure in the gas phase remains a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic, and bonding properties of [M16Ni24(CO)40]4– (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au20, owing that such species share a common tetrahedral [M16]4– central core with a 1S21P61D102S2 jellium configuration. In the case of Au20, the [Au16]4– core is capped by four Au+ ions, whereas in [M16Ni24(CO)40]4– it is capped by four Ni6(CO)10 units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M16]4– species must be capped for further stabilization. It follows that the Ni6(CO)10 units in [M16Ni24(CO)40]4– should not be considered as external ligands as their bonding with the [M16]4– core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M16Ni24(CO)40]4– species can be seen as the solution version of tetrahedral M20 clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M = Ag and Au and, particularly promising, with M = Cu. Furthermore, optical properties were simulated to assist future experimental characterization." @default.
• W2793642292 created "2018-03-29" @default.
• W2793642292 creator A5010883295 @default.
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• W2793642292 date "2018-02-15" @default.
• W2793642292 modified "2023-10-18" @default.
• W2793642292 title "[M₁₆Ni₂₄(CO)₄₀]^4–: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au₂₀ Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations" @default.
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• W2793642292 doi "https://doi.org/10.1021/acs.jpcc.8b00227" @default.
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