Ferrocene analogues of sandwich B12·Cr·B12: A theoretical study

Yuan, Yuan; Cheng, Longjiu

doi:10.1063/1.4773281

Cited by 24 publications

(7 citation statements)

References 72 publications

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“…Jena and co-workers attributed the anomalous stability of B 12 to a triple aromaticity: peripheral and central σ aromaticity and π aromaticity. Yuan and Cheng reported the AdNDP bonding pattern of B 12 which is shown in Figure . It is possible to observe nine 2c–2e σ bonds located at the periphery of the ring, three delocalized 4c–2e σ bonds located in the central part of the cluster, three 5c–2e bonds located in the outer B 9 ring, and three 7c–2e π bonds, clearly showing a triple aromaticity character according to Hückel’s rule .…”

Section: Resultsmentioning

confidence: 99%

Electronic Transmutation Concept: Is the Inverse Process Possible? An Evaluation of Main Group Compounds

2023

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The electronic transmutation (ET) concept states that when an element with atomic number Z gains an electron, it transmutes into a Z + 1 element, leading to species that possess similar chemical bonding patterns and geometric structures regarding the original (Z + 1) element. In this work, the opposite concept, that is, the inverse ET, is assessed. For this purpose, several main group compounds have been analyzed in terms of the adaptive natural density partitioning. The obtained results suggest that when an atom Z loses an electron, it transmutes into a Z − 1 atom, acquiring its geometrical structure and bonding pattern.

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Section: Resultsmentioning

confidence: 99%

Electronic Transmutation Concept: Is the Inverse Process Possible? An Evaluation of Main Group Compounds

2023

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“…Why is this tetrahedron cluster stable? First, we concentrate on the nature of the bonding in this structure by using AdNDP method which is wildly applied for closed-shell species recovering both the classical Lewis bonding concepts (lone-pairs and two-center two electron (2c-2e) bonds) and the delocalized n-center two electron (nc-2e) bonds [43][44][45][46][47][48][49][50][51][52][53] .…”

Section: Electronic Structurementioning

confidence: 99%

Electronic Stability of Eight-electron Tetrahedral Pd<sub>4</sub> Clusters

Shen¹,

Cheng²

2018

Acta Physico-Chimica Sinica

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Motivated by the unusual structure of the [Pd4(μ3-SbMe3)4(SbMe3)4] cluster, which is composed of a tetrahedral (Td) 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 Td [Pd4(μ3-SbH3)4(SbH3)4] cluster and a series of its analogues. The Td 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 sp 3 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 2esuperatoms. 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 1S 2 1P 6 electronic configuration. The density functional theory (DFT) calculations showed that the Td [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 d 10 •••d 10 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.

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“…68,75,76 The geometry optimizations are carried out with 6-31G* basis set for boron and LANL2DZ for trans-metal atoms. To confirmed the stability of the complexes, the binding energy, HOMO-LUMO gap, vertical electron affinity (VEA), vertical ionization potential (VIP), and vibrational frequency are also calculated on the TPSSh/6-31G*/LANL2DZ level of theory.…”

Section: Computational Detailsmentioning

confidence: 99%

Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8)

Cheng

Yang

2014

The Journal of Chemical Physics

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It is well known that double-ring boron clusters have got the special double aromaticity with delocalized π orbitals in two directions (tangential and radial), which are potential ligands centered by a transition metal. In this article, the transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8) are theoretically investigated by density functional theory calculations. These endohedral compounds have also got double aromaticity in both tangential and radial directions. Interestingly, the tangential delocalized π orbitals of boron ligands following the Huckle's (4n + 2) rule do not interact with the central metal, while the radial π orbitals of boron ligands are bonded with the central mental to form spd-π endohedral bonding. The spd-π endohedral bonding follows the 18e-principle in Ni@B14 and Fe@B16. However, due to the flat shape of the compounds, 14e (Cr@B14) and 16e (Ni@B12) can also be electronically very stable where the energy levels of the spd-π orbitals delocalized in z-direction rise up. This intriguing bonding model makes sense in further study of the boron chemistry.

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Ferrocene analogues of sandwich B12·Cr·B12: A theoretical study

Cited by 24 publications

References 72 publications

Electronic Transmutation Concept: Is the Inverse Process Possible? An Evaluation of Main Group Compounds

Electronic Transmutation Concept: Is the Inverse Process Possible? An Evaluation of Main Group Compounds

Electronic Stability of Eight-electron Tetrahedral Pd<sub>4</sub> Clusters

Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8)

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