Geometry and chemical bonding in polyhedral boranes, metallaboranes, and dimetallaboranes: From closo to isocloso to oblatocloso polyhedra

King, R. B.

doi:10.1016/j.jorganchem.2008.12.060

Cited by 6 publications

(2 citation statements)

References 28 publications

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“…These structures are generally slightly hypoelectronic with only n rather than n + 1 seps [20]. Later, even more hypoelectronic species (n − 3 seps) with highly oblate (flattened) structures called oblatocloso deltahedra in contrast to spherical or prolate geometry [21], were discovered [22,23] and rationalized [24][25][26][27][28][29]. In these structures, the metal atoms are generally highly connected and occupy opposite vertices in such a way, that the M-M distance is consistent with the existence of a cross-cluster bond.…”

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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Section: Introductionmentioning

confidence: 99%

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

2020

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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: 99%

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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Boron: Polyhedral Metallaboranes

Pathak

Mishra

Ghosh

2022

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Metallaborane clusters and their related chemistry were initially developed as a variant of metal–ligand coordination chemistry much along the lines of organometallic chemistry. However, owing to the insight imparted by the electron counting rules and isolobal analogy principle, the interconnections between apparently distinct molecules like polyhedral boranes and transition metal clusters were established. This certainly defined the scope of the area and notable advances toward the improvement of synthetic routes were witnessed. The advent of improved routes for synthesis widened the purview further by extending the limits of attainable sizes and geometries of polyhedral metallaboranes from diborane analogs to polyhedral cages of up to 12‐vertices to supraicosahedral and condensed cage macro‐polyhedral clusters. Wade–Mingos rules and Jemmis mno rule helped at gaining perspective about the unique structure and bonding present in this class of compounds. This article provides a brief overview of the syntheses and structural aspects in the context of electron counting rules of the most noted structural motifs assumed by polyhedral metallaboranes.

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Geometry and chemical bonding in polyhedral boranes, metallaboranes, and dimetallaboranes: From closo to isocloso to oblatocloso polyhedra

Cited by 6 publications

References 28 publications

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

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

Boron: Polyhedral Metallaboranes

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