Ba<sub>3</sub>As<sub>14</sub>, die erste Verbindung mit dem Cluster‐Anion As

Schmettow, Walter; Schnering, Hans Georg̀ von

doi:10.1002/ange.19770891212

Cited by 36 publications

(4 citation statements)

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“…Some of Zintl's ions have been subsequently isolated by fairly conventional means, for example, the barium salt of As73-by more direct, high-temperature reactions. 46 Even for tellurium where the stability of polyanions might be the most borderline among the chalcogenides Te32-, Te42-*2MeOH, Te52", and the novel i[Te4Te2/ 22-] have all been isolated.48-51 All of the polychalcogenide anions obtained in solution appear to be simple chain fragments and will not be considered further. Some ions reported by Zintl and not yet isolated involve higher charges per atom than in species obtained to date (Table II), As33-, Sb33-, Bi33-, As53-, and Bi53-,…”

Section: Isolation Of Zintl Anionsmentioning

confidence: 99%

Polyatomic Zintl anions of the post-transition elements

Corbett¹

1985

Chem. Rev.

486

280

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Section: Isolation Of Zintl Anionsmentioning

confidence: 99%

Polyatomic Zintl anions of the post-transition elements

Corbett¹

1985

Chem. Rev.

486

280

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“…The production of these cluster molecules served to open synthetic pathways for larger cluster systems with very interesting structures and reactivity patterns. A cluster of particular interest is [Bi 4 Fe 4 (CO) 13 ] 2- ([ 1 ] 2- ) , which has a novel cage structure reminiscent of Zintl anions such as E 7 3- (E = P, As, Sb) with some vertices replaced by transition metal fragments. − In order to understand the chemistry of this intriguing cluster, we have begun to probe its reactivity with a variety of reagents. In particular, we were interested in determining if the open Bi 3 face could be capped by an additional fragment.…”

Section: Introductionmentioning

confidence: 99%

Halide Ion Addition to Bismuth-Containing Iron Carbonyl Compounds: Synthesis and Characterization of the Two Bridged-Butterfly Cluster Compounds [Et₄N][(μ-H)Fe₂(CO)₆Bi₂{μ-Fe(CO)₄}] and [{PhCH₂NMe₃}{(μ-H)Fe₂(CO)₆Bi₂(μ-Cl)₂}]_∞ and Stabilization of Reduced-Hypervalent Bismuth Centers by Coordination to a Metal Center in [PhCH₂NMe₃]₃[Bi₃
Eveland
¹
,
Saillard
²
,
Whitmire
³

1997
Inorg. Chem.
17
1
1
0
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The reaction of [Q](2)[Bi(4)Fe(4)(CO)(13)] ([Q](2)[1]; [Q] = [Et(4)N](+), [PhCH(2)NMe(3)](+)) with MePCl(2) in MeCN is a complicated reaction which gives different results depending upon the stoichiometry of the reaction. At a ratio of 1:1.33 (cluster:phosphine), the reaction yields a mixture of the new bismuth-iron carbonyl compounds [Q][(&mgr;-H)Fe(2)(CO)(6)Bi(2){Fe(CO)(4)}] ([Q][2]), which has a tetrahedral Fe(2)Bi(2) core edge-bridged across the bismuth centers by an [Fe(CO)(4)](2)(-) fragment, and [Q](3)[Bi(3)Cl(4)(&mgr;-Cl)(4){Fe(CO)(3)}] ([Q](3)[3]), containing a reduced complex ion [Bi(3)Cl(8)](-) stabilized by coordination to an iron tricarbonyl fragment. Extended Hückel molecular orbital calculations on this unusual anion are consistent with each bismuth atom possessing the same reduced oxidation state of +2.33. The compound [Et(4)N][2] crystallizes in the triclinic space group P&onemacr; (No. 2) with a = 10.246(2) Å, b = 11.859(2) Å, c = 12.474(2) Å, alpha = 71.11(3) degrees, beta = 79.60(3) degrees, gamma = 76.37(3) degrees, V = 1384.7(4) Å(3), and Z = 2, while [PhCH(2)NMe(3)](3)[3].0.87Et(2)O was characterized in the orthorhombic space group Pbca (No. 61) with a = 20.801(4) Å, b = 19.937(4) Å, c = 25.480(5) Å, V = 10566.8(36) Å(3), and Z = 8. When the reaction is carried out at a ratio of 1:2, the novel hydride [{Q}{(&mgr;-H)Fe(2)(CO)(6)Bi(2){&mgr;-Cl}(2)}](infinity) ([{Q}{4}](infinity)) is isolated. This cluster also has a "tetrahedral" core, with the Bi-Bi vector bridged by a chloride ligand and the molecules joined into infinite polymeric chains in the solid state by the second intermolecularly-bridging chloride ligand. [{PhCH(2)NMe(3)}{4}](infinity) crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 7.864(2) Å, b = 22.465(4) Å, c = 13.797(3) Å, beta = 105.96(3) degrees, V = 2343.5(9) Å(3), and Z = 4. The metal framework of [4](-) is similar to that of [2](-) with the notable exception that the Bi-Bi bond present in [2](-) is missing in [4](-) because of the additional electrons provided by the chloride ions. At stoichiometries greater than 2:1, the previously reported [Fe(CO)(4)Bi(2)Cl(6)](2)(-) ion is formed.

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“…It has previously been predicted that saturated cycloarsanes prefer planar pentagons due to the negative strain energy of As 5 H 5 . However, the puckered five-membered arsenic ring is also quite stable and can serve as an important structural unit for different complex agglomerates, such as [As 7 ] 3– clusters, originally reported for the Ba 3 As 14 compound . The HOMO–LUMO energy gap for the latter configuration is very large, 4.03 eV (PBE0) or 4.42 eV (CAM-B3LYP).…”

Section: Resultsmentioning

confidence: 67%

“…One can also notice that the As–As distances in the ring vary by about 4 to 5% (2.36–2.47 Å, as shown in Table and Figure c). These values are very close to the doubled covalent radius of As (1.19(4) Å) and match well with the reported values for multiple Zintl phases with As–As bonding. ,,− …”

Section: Resultsmentioning

confidence: 82%

Structural Uniqueness of the [Nb(As₅)₂]^5– Cluster in the Zintl Phase Cs₅NbAs₁₀

et al. 2021

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The structure of the novel Zintl phase, Cs 5 NbAs 10 , is reported for the first time. This compound crystallizes in the monoclinic P2 1 /c space group (no. 14) with eight formula units per cell. The structure represents a unique atomic arrangement, constituting a new structure type with Wyckoff sequence e32. The most important structural element is the unprecedented [Nb(As 5 ) 2 ] 5− cluster anion, formed by a Nb atom enclosed between two As 5 rings. These nonaromatic cyclic species, formally [As 5 ] 5− , adopt an envelope conformation similar to that of cyclopentane. To date, it is only the second example of an [As 5 ] 5− ring with this conformation, reported in an inorganic solidstate compound. The bonding characteristics of the [Nb(As 5 ) 2 ] 5− cluster and the [As 5 ] 5− rings are thoroughly investigated using first-principles methods and discussed. Electronic band structure calculations on Cs 5 NbAs 10 suggest that this compound is a semiconductor with an estimated band gap of ca. 1.4 eV.

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Ba₃As₁₄, die erste Verbindung mit dem Cluster‐Anion As

Cited by 36 publications

References 4 publications

Polyatomic Zintl anions of the post-transition elements

Polyatomic Zintl anions of the post-transition elements

Structural Uniqueness of the [Nb(As₅)₂]^5– Cluster in the Zintl Phase Cs₅NbAs₁₀

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Ba3As14, die erste Verbindung mit dem Cluster‐Anion As

Cited by 36 publications

References 4 publications

Polyatomic Zintl anions of the post-transition elements

Polyatomic Zintl anions of the post-transition elements

Structural Uniqueness of the [Nb(As5)2]5– Cluster in the Zintl Phase Cs5NbAs10

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Ba₃As₁₄, die erste Verbindung mit dem Cluster‐Anion As

Structural Uniqueness of the [Nb(As₅)₂]^5– Cluster in the Zintl Phase Cs₅NbAs₁₀