Theoretical Treatment of Ligated Clusters Containing Transition Metals

Halet, J.‐F.; Saillard, Jean‐Yves

doi:10.1016/b978-0-08-097774-4.00936-0

Cited by 9 publications

(7 citation statements)

References 172 publications

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“…The density functional theory (DFT) calculations often play pivotal role to understand this apparent systematic rule deviation . The nature of the intermetallic interactions in the flattened dimetallaborane compounds (also termed as oblato-nido species) invoke speculations that has been dealt with several times in the literature by molecular orbital (MO) analysis. ,− The results seem to fully in agreement with some reports evidencing M–M single bond, with some others suggesting internal M–M double bond …”

Section: Introductionsupporting

confidence: 55%

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)₂B₄H₁₀] (M = Mo and W)

2018

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Thermolysis of mono metal carbonyl fragment, [M′(CO)5·thf, M′ = Mo and W, thf = tetrahydrofuran] with an in situ generated intermediate, obtained from the reaction of [Cp*MCl4] (M = Mo and W, Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with [LiBH4·thf], yielded dimetallaboranes, 1 and 2. Isolations of [{Cp*M(CO)}2B4H6] (M = Mo (1) and W(2)) provide direct evidence for the existence of saturated molybdaborane and tungstaborane clusters, [(Cp*M)2B4H10]. Our extensive theoretical studies together with the experimental observation suggests that the intermediate may be a saturated cluster [(Cp#M)2B4H10], not unsaturated [(Cp#M)2B4H8] (Cp# = Cp or Cp*), which was proposed earlier by Fehlner. Furthermore, in order to concrete our findings, we isolated and structurally characterized analogous clusters [(Cp*Mo)2(CO)(μ-Cl)B3H4W(CO)4] (3) and [(Cp*WCO)2(μ-H)2B3H3W(CO)4] (4). All the compounds have been characterized by solution-state 1H, 11B, IR, and 13C NMR spectroscopy, mass spectrometry, and the structural architectures of 1, 3, and 4 were unequivocally established by X-ray crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Both the Fenske–Hall and Kohn–Sham molecular orbital analyses showed an increased thermodynamic stability for [(Cp#M)2B4H10] compared to [(Cp#M)2B4H8]. Furthermore, large HOMO–LUMO gap and significant cross cluster M–M bonding have been observed for clusters 1–4.

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Section: Introductionsupporting

confidence: 55%

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)₂B₄H₁₀] (M = Mo and W)

2018

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“…Chemists know how the electronic structure and geometry of molecules are strongly imbricated. In essence, the electron count governs the shape of molecules because it relates to the closed-shell principle [2]. This principle states that, in general, any molecule is (thermodynamically and kinetically) stable when a significant energy gap separates the fully occupied molecular orbitals (MO) (generally the bonding or nonbonding ones) from the unoccupied MOs (generally the antibonding ones).…”

Section: Introductionmentioning

confidence: 99%

Polyhedral [M2B5] Metallaborane Clusters and Derivatives: An Overview of Their Structural Features and Chemical Bonding

2020

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A large number of metallaborane clusters and their derivatives with various structural arrangements are known. Among them, M2B5 clusters and derivatives constitute a significant class. Transition metals present in these species span from group 4 to group 7. Their structure can vary from oblatonido, oblatoarachno, to arachno type open structures. Many of these clusters appear to be hypoelectronic and are often considered as ‘rule breakers’ with respect to the classical Wade–Mingos electron counting rules. This is due to their unique highly oblate (flattened) deltahedral structures featuring a cross-cluster M−M interaction. Many theoretical calculations were performed to elucidate their electronic structure and chemical bonding properties. In this review, the synthesis, structure, and electronic aspects of the transition metal M2B5 clusters known in the literature are discussed. The chosen examples illustrate how, in synergy with experiments, computational results can provide additional valuable information to better understand the electronic properties and electronic requirements which govern their architecture and thermodynamic stability.

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“…Density functional theory (DFT) calculations have been able to sort out this apparent systematic rule deviation [7], but the proximity of the two metal atoms on opposite sides in the flattened direction allows some speculation about the nature of T-T interaction. This has been tackled several times in the literature using MO analysis [1,2,7,8,[12][13][14][15][16][17][18][19][20]. However, whereas the conclusions seem to fully converge with some studies evidencing a single T-T bond [7], some others suggest a formal internal T-T double bond [8].…”

Section: Introductionmentioning

confidence: 96%

Cross-cluster transition-metal bonding in oblato-nido dimetallaboranes unveiled by topological analysis

Boucher

Halet

Kohout

2015

Computational and Theoretical Chemistry

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The bonding situation for the oblato-nido dimetallaboranes (CpV)(2)B5H11 and (Cp*T)(2)B5H5+x, where T= Ta, Cr, Mo, W, Re and Cp*= C5Me5, was analyzed using the corresponding model series with Cp* replaced by the cyclopentadienyl C5H5. The application of different bonding indicators revealed that both through-space and through-bond (via boron atoms of the ring) interactions account for a substantial metal-metal bond. (C) 2015 Elsevier B.V. All rights reserved

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Theoretical Treatment of Ligated Clusters Containing Transition Metals

Cited by 9 publications

References 172 publications

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)₂B₄H₁₀] (M = Mo and W)

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)₂B₄H₁₀] (M = Mo and W)

Polyhedral [M2B5] Metallaborane Clusters and Derivatives: An Overview of Their Structural Features and Chemical Bonding

Cross-cluster transition-metal bonding in oblato-nido dimetallaboranes unveiled by topological analysis

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Theoretical Treatment of Ligated Clusters Containing Transition Metals

Cited by 9 publications

References 172 publications

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)2B4H10] (M = Mo and W)

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)2B4H10] (M = Mo and W)

Polyhedral [M2B5] Metallaborane Clusters and Derivatives: An Overview of Their Structural Features and Chemical Bonding

Cross-cluster transition-metal bonding in oblato-nido dimetallaboranes unveiled by topological analysis

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Resources

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Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)₂B₄H₁₀] (M = Mo and W)

Combined Experimental and Theoretical Investigations of Group 6 Dimetallaboranes [(Cp*M)₂B₄H₁₀] (M = Mo and W)