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

Boucher, Benoît; Halet, Jean‐François; Kohout, Miroslav

doi:10.1016/j.comptc.2015.06.029

Cited by 4 publications

(3 citation statements)

References 36 publications

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“…In clusters 2-4, computations indicated that the 11 B NMR chemical shifts of the boron atoms attached directly to the metal atoms (B2, B4, and B3, Figure 2) show a large systematic shift to higher field, whereas the chemical shifts at upper field for the boron atoms connected to the metal atoms via M−H−B bridged bonds (B1 and B5, Figure 2) hardly deviate from Cr to Mo to W species. The nature of the M-M interaction in clusters 2-6 and 8 was further probed using Cp-analog models employing the electron density and its derivatives within the framework of the QTAIM method and the aid of bonding indicators [70]. Results revealed that both through-space and through-bond (via boron atoms of the ring) interactions account for a substantial metal-metal interaction with a covalent bond order around 1.…”

Section: Electronic Structurementioning

confidence: 99%

“…The examples of this kind of M 2 B 5 species mostly range among the early transition metals such as group 5 in [(CpV) 2 B 5 H 11 ] [ 58 ] and [(Cp*Ta) 2 B 5 H 11 ] [ 59 ], group 6 in [(Cp*M) 2 B 5 H 9 ] (M = Cr, Mo, W) [ 60 , 61 , 62 , 63 , 64 , 65 ], and group 7 in [(Cp*Re) 2 B 5 Cl 5 H 2 ] [ 24 ] (Cp = C 5 H 5 , Cp* = C 5 Me 5 ). Due to their unique structure, thorough theoretical studies were performed by us and others in order to get some insight into their electronic structure and chemical bonding [ 66 , 67 , 68 , 69 , 70 ]. Later, many heterometallic [ 63 , 71 , 72 , 73 , 74 ] and chalcogenated derivatives of oblatonido-M 2 B 5 [ 75 , 76 , 77 , 78 ] were reported in the literature, which are isostructural as well as isoelectronic.…”

Section: Introductionmentioning

confidence: 99%

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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: Electronic Structurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

2020

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“…29 The experimentally observed oblatocloso structures, with the rhenium atoms located at approximately antipodal vertices, were very gratifyingly found to be the lowest energy structures. Subsequent theoretical studies by Halet and coworkers 30,31 have provided further insight into the metal-metal bonding in such structures. In addition, higher energy Cp 2 Re 2 B nÀ2 H nÀ2 isomers were found with adjacent rhenium vertices and short Re-Re distances suggesting surface multiple rhenium-rhenium bonds.…”

Section: Introductionmentioning

confidence: 99%