Structure and bonding in a bimetallic endohedral cage, [Co 2 @Ge 16 ] z−

Xiao, Jin; Espinoza-Quintero, Gabriela; Below, Benjamin; Arcisauskaite, Vaida; Goicoechea, José M.; McGrady, John E.

doi:10.1016/j.jorganchem.2015.03.032

Cited by 29 publications

(26 citation statements)

References 72 publications

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“…The extension of Zintl ion chemistry to clusters of higher nuclearity remains rather limited, and there are only a few known examples of endohedral germanium or tin clusters with two interstitial metal atoms. These include [Co 2 @Ge 16 ] 4– ,17 [M 2 @Sn 17 ] q – (M = Ni,18 a Co,5a,5b Pt18 b ), [Ni 2 @Sn 16 Ge] 4– ,6 a [Pd 2 @E 18 ] 4– (E = Ge, Sn)19 and [Ni 3 @Ge 18 ] 4– 6 b . In addition, a multiply endohedral structure [Sn@Cu 12 @Sn 20 ] 12– has been characterized in the intermetallic phases A 12 Cu 12 Sn 21 20.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3–, [Rh@Sn₁₂]^3–, [Rh₂@Sn₁₇]^6–and the first triply-fused stannide, [Rh₃@Sn₂₄]^5–

Liu

Xiao

et al. 2019

Chem. Sci.

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Section: Introductionmentioning

confidence: 99%

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3–, [Rh@Sn₁₂]^3–, [Rh₂@Sn₁₇]^6–and the first triply-fused stannide, [Rh₃@Sn₂₄]^5–

Liu

Xiao

et al. 2019

Chem. Sci.

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“…Very recently, Goicoechea et al. reported the bimetallic intermetalloid cluster [Co 2 @Ge 16 ] z− , which was characterized as a tetraanion in the solid state but as a monoanion according to the mass spectrum . However, its structure has not been elucidated due to the presence of severe positional disorder.…”

Section: Introductionmentioning

confidence: 99%

“…[19] Very recently,G oicoechea et al reported the bimetallic intermetalloid cluster [Co 2 @Ge 16 ] zÀ ,w hich was characterized as at etraanion in the solid state but as am onoanion accordingt ot he mass spectrum. [20] However,its structure has not been elucidated due to the presence of severe positional disorder. Auxiliary DFT calculations suggested that the isomer at the global mini-mum is the one with a D 2h -symmetric 3-connected structure, and the architecture is similar to the optimized geometry of Pd 2 @Si 16 .…”

Section: Introductionmentioning

confidence: 99%

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

Liu

Popov

et al. 2017

Chemistry A European J

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We report the successful isolation and structural elucidation of two bimetallic doped [Co @Ge ] clusters (α and β form), which were synthesized through the reaction of [{(ArN) CtBu}Co(η -toluene)] (Ar=2,6-diisopropylphenyl) and K Ge in ethylenediamine (en) solution and co-crystallized together in [K(2,2,2-crypt)] [Co @Ge ]⋅en. The α-[Co @Ge ] isomer prefers a distinct D 3-connected architecture, whereas the deltahedral isomeric β-[Co @Ge ] isomer adopts a quasi-C geometry and can be seen as coupling of two distorted arachno-[Co@Ge ] units. Chemical bonding analyses indicate that the skeleton of the α isomer is mainly composed of localized bonds, whereas only multicenter bonding interactions govern the geometry of the β isomer, which was further found to exhibit a fluxional behavior. The coexistence of both isomers within one unit cell links the 3-connected clusters with their deltahedral congeners, thus highlighting the structural and electronic flexibility of such discreet cluster systems.

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“…X-ray experiments that were supported by density functional theory (DFT) computations, pointed out that [Co 2 @Ge 16 ] 4− exists in two different isomers in which both Co atoms are encapsulated by Ge 16 cages. 18,19 Beside such deltahedral structures, singly transition metaldoped germanium clusters provide us with a wide range of geometrical features. It is peculiar that the singly doped CoGe 10 3− and FeGe 10 3− clusters are stable in a double-ring tube in which either the Co or the Fe atom is centered in a D 5h (5/5) Ge 10 pentagonal prism.…”

Section: Introductionmentioning

confidence: 99%

B_xGe₁₂^0/+ Clusters with x = 1–4: Germanium Tubes Stabilized by Three and Four Boron Dopants

et al. 2019

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Some boron-doped germanium clusters B x Ge 12 q with x = 1, 2, 3, and 4 and q = 0, 1 were designed as stabilized double ring tubes. While the B 2 Ge 12 constitutes the smallest deltahedral germanium cluster, both B 3 Ge 12 + and B 4 Ge 12 clusters present us, for the first time, with an endohedral tubular motif in which either the B 3 or the B 4 cycle is encapsulated inside a Ge 12 hexagonal prism tube. Both B 3 and B 4 units thus satisfy a geometry requirement to create an endohedral structure within the Ge 12 double ring. Keeping their high symmetry, both B 3 and B 4 units generate delocalized bonds upon interaction with the Ge 12 tubular framework and thereby induce an aromatic character for the resulting B 3 Ge 12 + and B 4 Ge 12 , respectively. Their aromaticity was probed by the magnetic responses of electron densities. Such a tubular aromaticity appears to greatly contribute to the high thermodynamic stability of the binary hexagonal germanium tubes.

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Structure and bonding in a bimetallic endohedral cage, [Co 2 @Ge 16 ] z−

Cited by 29 publications

References 72 publications

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3–, [Rh@Sn₁₂]^3–, [Rh₂@Sn₁₇]^6–and the first triply-fused stannide, [Rh₃@Sn₂₄]^5–

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3–, [Rh@Sn₁₂]^3–, [Rh₂@Sn₁₇]^6–and the first triply-fused stannide, [Rh₃@Sn₂₄]^5–

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

B_xGe₁₂^0/+ Clusters with x = 1–4: Germanium Tubes Stabilized by Three and Four Boron Dopants

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Structure and bonding in a bimetallic endohedral cage, [Co 2 @Ge 16 ] z−

Cited by 29 publications

References 72 publications

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn10]3–, [Rh@Sn12]3–, [Rh2@Sn17]6–and the first triply-fused stannide, [Rh3@Sn24]5–

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn10]3–, [Rh@Sn12]3–, [Rh2@Sn17]6–and the first triply-fused stannide, [Rh3@Sn24]5–

[Co2@Ge16]4−: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

BxGe120/+ Clusters with x = 1–4: Germanium Tubes Stabilized by Three and Four Boron Dopants

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Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3–, [Rh@Sn₁₂]^3–, [Rh₂@Sn₁₇]^6–and the first triply-fused stannide, [Rh₃@Sn₂₄]^5–

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3–, [Rh@Sn₁₂]^3–, [Rh₂@Sn₁₇]^6–and the first triply-fused stannide, [Rh₃@Sn₂₄]^5–

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

B_xGe₁₂^0/+ Clusters with x = 1–4: Germanium Tubes Stabilized by Three and Four Boron Dopants