A new family of 14-vertex hexacapped metal cubes with main group IV (14) atoms: synthesis and structural-bonding analysis of Ni9(.mu.4-GeEt)6(CO)8 containing a nickel-centered Ni8(.mu.4-Ge)6 cubic cage with an unusual electron count

Zebrowski, Jeffrey P.; Hayashi, Randy K.; Bjarnason, Ásgeir; Dahl, Lawrence F.

doi:10.1021/ja00034a060

Cited by 37 publications

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“…A typical example of this closed-shell count is Ni 9 (µ 4 -GeEt) 6 (CO) 8 . [18] However, it has also been shown that in the particular case where E is a bare main-group atom, the 124-MVE closedshell configuration is not always ensured, due to the lone pair effect of the bare µ 4 -E atom. Indeed, these lone pairs, which span into a 1g + t 1u + e g combinations in the cluster O h symmetry, tend to destabilize the occupied cluster levels of the same symmetries, especially in the case of heavy maingroup E atoms which have diffuse lone pairs, able to provide long distance overlap.…”

Section: Electronic Structures Of [3]mentioning

confidence: 99%

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

et al. 2008

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International audienceExtended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]-/[3]2-/[3]3-/[3]4-/[3]5- regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]- containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ-Te). A neutral cluster comprising the Co@Co8(μ4-Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X-ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to -5) family and on related species indicate that there is no significant Jahn-Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]- is a spin triplet with spins interacting antiferromagnetically in a 1D space

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Section: Electronic Structures Of [3]mentioning

confidence: 99%

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

et al. 2008

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“…[1] Clusters of the type [M 9 L 8 (m 4 -E) 6 ] (M Ni, Pd; L PPh 3 , CO, Cl; E GeEt, [2] As, [3] Sb, [4] Te [5] ) are characterized by an additional metal atom in the center of the cluster. The first cobalt-containing representative of the [M 9 L 8 (m 4 -E) 6 ] class of compounds is the cluster salt [(C 5 Me 5 ) 2 Nb(CO) 2 ] 2 [Co 9 (CO) 8 Te 6 ] ([(C 5 Me 5 ) 2 Nb(CO) 2 ] 2 (1)), which was only obtained in very low yields, so that it is impossible to further investigate its chemical properties.…”

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confidence: 99%

“…The reaction of [Cp' 2 Nb(Te 2 )H] (Cp' tBuC 5 H 4 ) [7] with two equivalents of [Co 2 (CO) 8 ] in boiling toluene gave the dark red neutral compound [{Cp' 2 Nb(CO)} 3 Co 9 (CO) 8 Te 6 ] (2) in good yield after chromatographic work-up on silica gel. As mass spectra of 2 could not be obtained, its composition was derived from an X-ray diffraction analysis of the Cr(CO) 5 -adduct 3 (see below) and confirmed by C, H analyses.…”

mentioning

confidence: 99%

[{(tBuC5H4)2Nb(CO)}3Co9(CO)8Te6⋅3 Cr(CO)5]: Unusual Stabilization of a Cubic Body-Centered Metal Telluride Cluster by Peripheral Complex Fragments

Brunner¹,

Stückl²,

Wächter³

et al. 2001

Angew. Chem. Int. Ed.

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“…This is not actually the case [45]. There is only one example among the characterized M 9 compounds, namely Ni9(/24-GeEt)6(CO) 8 [38], the electronic structure of which fits with one of the electronic structures shown in Fig. 3.…”

Section: D) the Strength Of The Ms-m I And Ms-m S Bonds Will Depend mentioning

confidence: 87%

“…The 124-MVE compound Ni9(/14-GeEt)6(CO) 8 (6) characterized by Dahl and coworkers provides a specific example [38]. Several metal-centered hexacapped cubic M9(P4-E)6L 8 clusters analogous to 6 have been structurally characterized.…”

Section: Metal-centered Hexacapped Mg(/j4-e)6l 8 Speciesmentioning

confidence: 99%

Electron count versus structural arrangement in clusters based on a cubic transition metal core with bridging main group elements

Halet

Saillard

Structural and Electronic Paradigms in Cluster Chemistry

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The bonding of diverse molecular clusters based on a cubic transition metal core with bridging main group elements is reviewed. It is shown that the cluster topology of these compounds is dependent on several parameters which can be calibrated. A large range of electron counts is generally observed without alteration of the cubic architecture. Examination of their electronic structures indicates that these species are at the borderline between molecular and solid states, characterized either by a closed-shell electronic configuration secured by a significant HOMO-LUMO gap, or by a quasi-continuous energy level structure often associated with open-shell electronic configurations.

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A new family of 14-vertex hexacapped metal cubes with main group IV (14) atoms: synthesis and structural-bonding analysis of Ni9(.mu.4-GeEt)6(CO)8 containing a nickel-centered Ni8(.mu.4-Ge)6 cubic cage with an unusual electron count

Cited by 37 publications

References 0 publications

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

[{(tBuC5H4)2Nb(CO)}3Co9(CO)8Te6⋅3 Cr(CO)5]: Unusual Stabilization of a Cubic Body-Centered Metal Telluride Cluster by Peripheral Complex Fragments

Electron count versus structural arrangement in clusters based on a cubic transition metal core with bridging main group elements

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A new family of 14-vertex hexacapped metal cubes with main group IV (14) atoms: synthesis and structural-bonding analysis of Ni9(.mu.4-GeEt)6(CO)8 containing a nickel-centered Ni8(.mu.4-Ge)6 cubic cage with an unusual electron count

Cited by 37 publications

References 0 publications

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters

[{(tBuC5H4)2Nb(CO)}3Co9(CO)8Te6⋅3 Cr(CO)5]: Unusual Stabilization of a Cubic Body-Centered Metal Telluride Cluster by Peripheral Complex Fragments

Electron count versus structural arrangement in clusters based on a cubic transition metal core with bridging main group elements

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Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters

Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co₉Te₆(CO)₈ Clusters