八电子Pd4四面体团簇的电子结构稳定性分析

doi:10.3866/PKU.WHXB201712151

Abstract

Abstract:

Motivated by the unusual structure of the [Pd₄(μ₃-SbMe₃)₄(SbMe₃)₄] cluster, which is composed of a tetrahedral (T_d) Pd(0) core with four terminal SbMe₃ ligands and four triply bridging SbMe₃ ligands capping the four triangular Pd₃ faces (J. Am. Chem. Soc. 2016, 138, 6964), we performed a computational study of the structure and bonding characteristics of the T_d [Pd₄(μ₃-SbH₃)₄(SbH₃)₄] cluster and a series of its analogues. The T_d structure of the [Pd₄(μ₃-SbH₃)₄(SbH₃)₄] cluster could be explained by the cluster electron-counting rules based on the 18-electron rule for transition-metal centers; each sp³ hybridized Pd atom contributed ten valence electrons, and eight valence electrons were provided by one terminal SbH₃ and three bridging μ₃-SbH₃ ligands. The [Pd₄(μ₃-SbH₃)₄(SbH₃)₄] cluster had a count of 104 valence electrons in total; chemical bonding analysis indicated that the cluster featured twenty electron lone pairs generated by d orbital of the four Pd atoms, twenty-four Sb―H σ bonds, four terminal Pd―Sb σ bonds, and four delocalized bonds. There were two bonding patterns of the eight delocalized electrons between the four capping Sb atoms and the Pd₄ core. The first pattern was based on the superatom-network (SAN) model, whereby the palladium cluster could be described as a network of four 2e^– superatoms. The second pattern was based on the spherical jellium model, whereby the cluster could be rationalized as an 8e^– [Pd₄(μ₃-SbH₃)₄] superatom with 1S²1P⁶ electronic configuration. The density functional theory (DFT) calculations showed that the T_d [Pd₄(μ₃-SbH₃)₄(SbH₃)₄] cluster had a large HOMO-LUMO (HOMO: highest occupied molecular orbital; LUMO: lowest unoccupied molecular orbital) energy gap (2.84 eV) and a negative nucleus-independent chemical shift (NICS) value (-12) at the center of the [Pd₄(μ₃-SbH₃)₄(SbH₃)₄] cluster, indicating its high chemical stability and aromaticity. Furthermore, the NICS values in the range of 0–0.30 nm of the [Pd₄(μ₃-SbH₃)₄] motifs were much more negative than those of [Pd₄(SbH₃)₄] in the same range, revealing that the overall stability of [Pd₄(μ₃-SbH₃)₄(SbH₃)₄] was likely derived from the local stability of Pd₄(μ₃-SbH₃)₄. Meanwhile, the d¹⁰…d¹⁰ interaction played a critical role in stabilizing the Pd₄ tetrahedron structure, which is similar to the aurophilicity in Au-Au clusters. It was also found that there is a large difference in the stability of transition metal and non-transition metal clusters with a tetrahedron structure. The structures and bonding patterns of the designed analogues were similar to those of [Pd₄(μ₃-SbH₃)₄(SbH₃)₄]. To summarize, this study was relevant for deciphering the nature of the bonds in a tetrahedral complex with four cores and eight ligands, and predicting a series of analogues. It is expected that this work will provide more options for the synthesis of tetrahedral 4-core transition metal compounds.

Key words: Metal cluster, Super valence bond, Superatom, Chemical bonding analysis, Closed-shell interaction, Aromaticity

Yanfang SHEN,Longjiu CHENG. Electronic Stability of Eight-electron Tetrahedral Pd₄ Clusters[J].Acta Phys. -Chim. Sin., 2018, 34(7): 830-836.

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Electronic Stability of Eight-electron Tetrahedral Pd₄ Clusters

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