Al22Br20⋅12 THF: das erste polyedrische Aluminiumsubhalogenid – ein Schritt auf dem Weg zu einer neuen Aluminiummodifikation?

Klemp, Christoph; Köppe, Ralf; Weckert, E.; Schnöckel, Hansgeorg

doi:10.1002/(sici)1521-3757(19990614)111:12<1851::aid-ange1851>3.0.co;2-q

Cited by 51 publications

(13 citation statements)

References 30 publications

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“…In contrast, in the case of the only previously obtained Ga 22 cluster with an icosahedral Ga 22 core (without a central Ga atom), [Ga 22 {N(SiMe 3 ) 2 } 10 Br 10 ] 2− ( 3 ),6 the average oxidation number of 0.82 is not very different from that of the GaX starting material. This is also true for the first polyhedral gallium subhalide [Ga 24 X 22 ] ( 4 )7 (average oxidation number 0.92), which can be viewed as a common precursor (possibly in a slightly modified form, such as [Ga 22 X 20 ], which is analogous to the well‐known [Al 22 X 20 ]8) for the numerous Ga 22 clusters (Figure 1). With the P t Bu 2 ligand used here, as in previous cases such as the metalloid clusters [Ga 16 (P t Bu 2 ) 10 ] ( 5 )9 and [Ga 51 (P t Bu 2 ) 14 Br 6 ] 3− ( 6 ),10 we find that the cluster core is linked to the outer shell by additional bonds to bridging P atoms, which facilitates the isolation of unusual Ga n frameworks.…”

Section: Calculated Atomic Volumes In Icosahedral and Body‐centered Cmentioning

confidence: 71%

[Ga₂₂(PtBu₂)₁₂]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

2004

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Dedicated to Professor Nils Wiberg on the occasion of his 70th birthdayWith the formation of three different Ga 22 frameworks in metalloid clusters, the element gallium assumes a unique position in the field of metal clusters, [1] since to our knowledge, structural isomers of large metalloid clusters are not known to date for any other metal. Here we report an additional structural variation in the arrangement of 22 gallium atoms, in which for the first time an icosahedral Ga 12 core is retained despite extensive reduction of the Ga 22 framework (average oxidation number 0.55). We have previously achieved low oxidation numbers for Ga 22 clusters only when gallium-centered arrangements were present in the cluster core (oxidation number 0.36, Figure 1): [Ga 22 R 8 ] (1) with R = SitBu 3 (1 a), [2] Si(SiMe 3 ) 3 (1 b), [3] and Ge(SiMe 3 ) 3 (1 c) [4] as well as [Ga 22 R 10 ] 2À (2) with R = N(SiMe 3 ) 2 ; [5] the coordination numbers of the central Ga atoms are 13 for 1 and 11 for 2. In contrast, in the case of the only previously obtained Ga 22 cluster with an icosahedral Ga 22 core (without a central Ga atom), [Ga 22 {N(SiMe 3 ) 2 } 10 Br 10 ] 2À (3), [6] the average oxidation number of 0.82 is not very different from that of the GaX starting material. This is also true for the first polyhedral gallium subhalide [Ga 24 X 22 ] (4) [7] (average oxidation number 0.92), which can be viewed as a common precursor (possibly in a slightly modified form, such as [Ga 22 X 20 ], which is analogous to the well-known [Al 22 X 20 ] [8] ) for the numerous

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Section: Calculated Atomic Volumes In Icosahedral and Body‐centered Cmentioning

confidence: 71%

[Ga₂₂(PtBu₂)₁₂]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

2004

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“…GaBr (48 mmol) was cocondensed with toluene (100 mL) and THF (5 mL) according to the literature method 5. A portion (25 ml) of the ca.…”

Section: Methodsmentioning

confidence: 99%

“…Although we have recently synthesized a series of metalloid gallium clusters from GaX‐solution (X=Cl, Br, I),2, 3 no further examples of Gallium subhalides have been reported 4. However, we have shown that the polyhedral aluminum subhalide, [Al 22 X 20 ]⋅12 THF ( 1 ; X=Cl, Br) can be prepared from metastable AlCl or AlBr solution 5. 6 The topology of the 22 aluminium atoms in 1 is unexpected: 10 aluminium atoms are directly bonded by 2c–2e bonds to a central Al 12 icosahedron such that two aluminum atoms at the apexes of the Al 12 icosahedron are “naked”.…”

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confidence: 99%

The Polyhedral Gallium Subhalide [Ga₂₄Br₂₂]⋅10 THF: The First Step on the Path to a New Modification of Gallium?

et al. 2004

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“…3) In several earlier publications we discussed to what degree the topology of metalloid clusters can be interpreted as snapshots in the formation of hypothetical modifications of the metals 15. 31, 32 Exemplarily, a supposedly nonmetallic modification of Al with an α‐boron structure shall be mentioned 33. 34 Here we want to study only clusters that contain a core of 12 Ga atoms.…”

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A Metalloid [Ga₂₃{N(SiMe₃)₂}₁₁] Cluster: The Jellium Model Put to Test

et al. 2007

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Dedicated to Professor Helge Willner on the occasion of his 60th birthdayDepicting the electronic structure of compounds clearly is one of the most difficult tasks in chemistry. For molecular moieties of identical atoms (clusters) many models have been developed which are often limited to specific compound classes. Gaseous cluster species, for example, as ions in mass spectrometry, could suitably be described with the Jellium model because the filling of electronic shells in these species, like in atoms, with specific numbers of valence electrons can explain their different stabilities.[ (Figure 1). [6,7] The rules of Wade, [9] Mingos, [10] Zintl, [11] Klemm, [11] and Jemmis, [12] for example, were useful in the explanation of bonding found in the structurally characterized cluster species of boranes or Zintl ions. But these models can only rudimentarily be applied to larger cluster species of identical metal atoms [13] (for example [Al 77 R 20 ] 2À ). The topological similarity in the arrangement of metal atoms of these clusters with the one found in elements was our motivation for terming such species metalloid or even elementoid clusters. [14,15] Recently King and Schleyer could show that some of the mentioned rules can in fact be used in the bond description of such a metalloid [Ga 22 R 8 ] cluster (Figure 1). [16] Herein, we attempt to demonstrate that the Jellium model can also contribute to the understanding of several metalloid clusters. These considerations are now possible for the first time because a unique possibility of comparison for a single element is given by a {Ga 23 } cluster presented here and four further differently structured {Ga 22 } clusters, [17] as well as a recently reported {Ga 24 } cluster [8] (Figure 1). The capacity of the Jellium model to describe the bonding of such clusters can be assessed based on experimental structural data. For the discussion on the bonding situation special attention will be given to the atomic volumes.At À78 8C a suspension of LiN(SiMe 3 ) 2 in toluene was treated with a small excess of a metastable GaCl solution in toluene/ether (3:1) that was obtained by the joint condensation of GaCl molecules formed at about 900 8C and the solvent mixture.[18] After processing the reaction solution (see the Experimental Section) black rhombus-shaped crystals of the title compound [Ga 23 {N(SiMe 3 ) 2 } 11 ] (1) were obtained. [19] Thus, formally, disproportionation and subsequent or simultaneous metathesis of GaCl occurred in the reaction.The result of the X-ray structural analysis of 1 is presented in Figure 2 a.[20] A body-centered naked {Ga 12 } core is present in 1 and is surrounded by 11 GaR moieties. The most important structural data are shown in the caption of Figure 2, where 1 is contrasted with the similar cluster [Ga 22 {N(SiMe 3 ) 2 } 10 ] 2À (2).[21] Both clusters contain a central Ga atom uncommonly surrounded by 11 further "naked" (that is, not ligand-bearing) gallium atoms.[22] The ligand shell of 1 is formed by 11 GaR moieties, and that of 2 is for...

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Al22Br20⋅12 THF: das erste polyedrische Aluminiumsubhalogenid – ein Schritt auf dem Weg zu einer neuen Aluminiummodifikation?

Cited by 51 publications

References 30 publications

[Ga₂₂(PtBu₂)₁₂]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

[Ga₂₂(PtBu₂)₁₂]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

The Polyhedral Gallium Subhalide [Ga₂₄Br₂₂]⋅10 THF: The First Step on the Path to a New Modification of Gallium?

A Metalloid [Ga₂₃{N(SiMe₃)₂}₁₁] Cluster: The Jellium Model Put to Test

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Al22Br20⋅12 THF: das erste polyedrische Aluminiumsubhalogenid – ein Schritt auf dem Weg zu einer neuen Aluminiummodifikation?

Cited by 51 publications

References 30 publications

[Ga22(PtBu2)12]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

[Ga22(PtBu2)12]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

The Polyhedral Gallium Subhalide [Ga24Br22]⋅10 THF: The First Step on the Path to a New Modification of Gallium?

A Metalloid [Ga23{N(SiMe3)2}11] Cluster: The Jellium Model Put to Test

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[Ga₂₂(PtBu₂)₁₂]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

[Ga₂₂(PtBu₂)₁₂]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique Case in the Field of Metalloid Clusters?

The Polyhedral Gallium Subhalide [Ga₂₄Br₂₂]⋅10 THF: The First Step on the Path to a New Modification of Gallium?

A Metalloid [Ga₂₃{N(SiMe₃)₂}₁₁] Cluster: The Jellium Model Put to Test