Synthesis, Structure, and Bonding of a Molecular Metalloid Ga<sub>19</sub> Cluster Anion

Schnepf, Andreas; Stösser, and G.; Schnöckel, Hansgeorg

doi:10.1021/ja000990o

Cited by 99 publications

(104 citation statements)

References 22 publications

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“…[3][4][5][6][7] Two milestones in aluminum-organic chemistry with a polyhedral {Al n }-lattice are [Al 12 R 12 ] 2À (1 2À ) [8] and [Al 4 Cp* 4 ] (2; Cp* = C 5 Me 5 ) [9][10][11] (Figure 1). The polyhedral closo-cluster 1 2À is an exception compared to the common low-valent aluminum and gallium clusters which tend to be so-called metalloid clusters.…”

Section: In Memory Of Earl Leonard Muettertiesmentioning

confidence: 99%

From Icosahedral Boron Subhalides to Octahedral Metalloid Aluminum and Gallium Analogues: Quo vadis, Wade's Rules?

2007

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The synthesis and characterization of polyhedral boron hydrides [1] and boron subhalides, [2] originally regarded as curios, at a second glance have proved to be a lucky chance for progress in chemistry, as on this basis new concepts of chemical bonding were developed, e. g. the Wade-Mingos rules. [3][4][5][6][7] Two milestones in aluminum-organic chemistry with a polyhedral {Al n }-lattice are [Al 12 R 12 ] 2À (1 2À ) [8] and [Al 4 Cp* 4 ] (2; Cp* = C 5 Me 5 ) [9][10][11] (Figure 1). The polyhedral closo-cluster 1 2À is an exception compared to the common low-valent aluminum and gallium clusters which tend to be so-called metalloid clusters.[12] These are clusters mainly characterized by the fact that the topology of the "naked", that is, non-ligand bearing cluster atoms in the cluster core, in many cases reflects the topology of the atoms found in metals and elements, respectively. [13][14][15] Prior to presenting the results of quantum chemical calculations for some [M 12 X 12 ] and [M 13 X 12 ] (M = B, Al, Ga; X = halide) model compounds, we describe our most recent experimental findings which prompted us to start these investigations: [16] Mass spectrometric examinations of the structurally known metalloid-cluster anion [Ga 13 (GaR À (3 À ). [16][17][18] This anion formed during the stepwise reaction of chlorine in the gas phase and as a result of the cleavage of six GaCl moieties [Eq (1)]. The isomer 3 À , when generated from density functional theory (DFT) calculations is, with its octahedral {Ga 6 } core, 30 kJ mol À1 more stable than the icosahedral molecule with a {Ga 12 } core and 12 terminally bound ligands that would be expected according to Wades rules. Based on these surprising results [16, 19] we have performed DFT calculations to elaborate some fundamental differences between typical Wade clusters in boron chemistry and metalloid clusters in aluminum and gallium chemistry.We have examined neutral and dianionic compounds of the structure [M 12 Cl 12 ] 0,2À (M = B, Al, Ga) to determine which of the two structural patterns (icosahedral M 12 -units or clusters with an M 6 -core) is energetically favored for the particular element. For each species we calculated the isomer with an icosahedral structure and terminally bound ligands (ico) and the isomer with an octahedral core of "naked" metal atoms (hence the term "metalloid" (m)). For the metalloid clusters (m), a protecting shell results consisting of doubly oxidized MX 2 units; the bridging (M-X-M) unit contributes to the stabilization of the cluster. The energetic relations between all isomers are shown in Figure 2. Selected structural parameters of [B 12 Cl 12 ] (4), [B 12 The energy diagram (Figure 2) depicts the differences between boron-, aluminum-, and gallium clusters: The icosahedral species 4 (ico) and 4 2À (ico) are energetically favored by 600 kJ mol À1 and 918 kJ mol À1 , respectively, over the metalloid isomers 4 (m) and 4 2À (m). On the other hand, the neutral metalloid Al and Ga clusters 5 (m) and 6 (m) are,

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Section: In Memory Of Earl Leonard Muettertiesmentioning

confidence: 99%

From Icosahedral Boron Subhalides to Octahedral Metalloid Aluminum and Gallium Analogues: Quo vadis, Wade's Rules?

2007

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“…[5] Der neue oktaedrische geschlossenschalige 18-Elektronen-Komplex [Mo(GaCp*) 6 ] (2) (R = C(SiMe 3 ) 3 ) zum Vergleich herangezogen werden. [15] Dieses spezielle Beispiel enthält einen Ga 13 À -Kern und sechs flächenverbrückende GaR-Zweielektonenliganden mit einer Gesamtelektronenzahl von 52. Es wird allgemeinhin akzeptiert, dass Struktur und Bindung solcher metalloiden Cluster nicht einfach über Elektronzahlregeln verstanden werden können; vielmehr muss jeder Fall individuell studiert werden.…”

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Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

et al. 2008

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“…[29] 4 (6) sein, einem kristallgraphisch charakterisierten Zwischenprodukt der Synthese von 3. [9,30] Bemerkenswert an 5 ist, dass sich Si in einer Tetraederlücke befindet, d. h., dass keine Substitution von Al durch Si stattfindet wie z.…”

Section: Professor Heinrich Nöth Zum 80 Geburtstag Gewidmetunclassified

Si@Al₅₆[N(2,6‐iPr₂C₆H₃)SiMe₃]₁₂ – der größte neutrale metalloide Aluminiumcluster: ein molekulares Modell für eine Si‐arme Al‐Si‐Legierung?

et al. 2008

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Si mittendrin: Si‐dotierte Al44‐Superatome bilden ein kubisch‐primitives Kristallgitter (siehe Bild; • Al, • Si) in dem Cluster Si@Al56[N(Dipp)SiMe3]12 , der ausgehend von einer metastabilen AlCl‐Lösung und dem Si‐haltigen Liganden N(Dipp)SiMe3 hergestellt wurde (Dipp=2,6‐iPr2C6H3). Das zentrale Si‐Atom hat drastische Auswirkungen auf die Struktur und Bindungsverhältnisse des Clusters.

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Synthesis, Structure, and Bonding of a Molecular Metalloid Ga₁₉ Cluster Anion

Cited by 99 publications

References 22 publications

From Icosahedral Boron Subhalides to Octahedral Metalloid Aluminum and Gallium Analogues: Quo vadis, Wade's Rules?

From Icosahedral Boron Subhalides to Octahedral Metalloid Aluminum and Gallium Analogues: Quo vadis, Wade's Rules?

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

Si@Al₅₆[N(2,6‐iPr₂C₆H₃)SiMe₃]₁₂ – der größte neutrale metalloide Aluminiumcluster: ein molekulares Modell für eine Si‐arme Al‐Si‐Legierung?

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Synthesis, Structure, and Bonding of a Molecular Metalloid Ga19 Cluster Anion

Cited by 99 publications

References 22 publications

From Icosahedral Boron Subhalides to Octahedral Metalloid Aluminum and Gallium Analogues: Quo vadis, Wade's Rules?

From Icosahedral Boron Subhalides to Octahedral Metalloid Aluminum and Gallium Analogues: Quo vadis, Wade's Rules?

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH3)9(ZnCp*)3]

Si@Al56[N(2,6‐iPr2C6H3)SiMe3]12 – der größte neutrale metalloide Aluminiumcluster: ein molekulares Modell für eine Si‐arme Al‐Si‐Legierung?

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Synthesis, Structure, and Bonding of a Molecular Metalloid Ga₁₉ Cluster Anion

Zwölf Einelektronenliganden koordinieren an ein Metallzentrum: Struktur und Bindung von [Mo(ZnCH₃)₉(ZnCp*)₃]

Si@Al₅₆[N(2,6‐iPr₂C₆H₃)SiMe₃]₁₂ – der größte neutrale metalloide Aluminiumcluster: ein molekulares Modell für eine Si‐arme Al‐Si‐Legierung?