The Last of the Five: the Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta6}Br12]Br3[TaBr6]0.86

Habermehl, Katja; Mudring, Anja‐Verena; Meyer, Gerd

doi:10.1002/ejic.201000581

Cited by 5 publications

(8 citation statements)

References 19 publications

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“…Ta6Br15(TaBr6)0.86, formerly known as the elusive "TaBr3", was reported in 2010 by Habermehl et al [35]. This cluster compound crystallizes in the trigonal symmetry space group 3 ̅ (No.…”

Section: Ta6br15(tabr6)-typementioning

confidence: 97%

“…This cluster compound crystallizes in the trigonal symmetry space group 3 ̅ (No. 167) with unit cell parameters a = 12.9860(11) Å and c = 33.285(4) Å [35]. Tantalum atoms arising from the cluster are located on one 36f crystallographic site, bromine atoms corresponding to inner ligands are located on two independent 36f sites, and bromine atoms corresponding to apical ligands are located on one 18e site.…”

Section: Ta6br15(tabr6)-typementioning

confidence: 99%

“…Tantalum atoms arising from the cluster are located on one 36f crystallographic site, bromine atoms corresponding to inner ligands are located on two independent 36f sites, and bromine atoms corresponding to apical ligands are located on one 18e site. Tantalum and bromine atoms arising from the TaBr6 complex occupied the 6a site and one 36f site, respectively, both with SOF of 0.861(13) [35]. Tantalum in the (TaBr6) complex is assumed to be pentavalent, suggesting that Ta6Br15(TaBr6)0.86 should be a salt formed by the association of (TaBr6) 0.86complexes and [Ta6Br15] 0.86+ cluster units [35].…”

Section: Ta6br15(tabr6)-typementioning

confidence: 99%

“…Tantalum and bromine atoms arising from the TaBr6 complex occupied the 6a site and one 36f site, respectively, both with SOF of 0.861(13) [35]. Tantalum in the (TaBr6) complex is assumed to be pentavalent, suggesting that Ta6Br15(TaBr6)0.86 should be a salt formed by the association of (TaBr6) 0.86complexes and [Ta6Br15] 0.86+ cluster units [35]. Hence, for a full occupation of the interstitial sites by TaBr6 complexes, a VEC of 14 is expected for the [Ta6Br i 12] 4+ cluster core [35].…”

Section: Ta6br15(tabr6)-typementioning

confidence: 99%

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Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-Dimensional Frameworks: A Review on Their Crystallographic and Electronic Structures

Lemoine

Halet

Cordier

2019

Structure and Bonding

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This review summarizes the development of the rich crystal and bonding chemistry of facecapped and edge-bridged inorganic niobium and tantalum octahedral cluster halide compounds, with a particular emphasis on those showing three-dimensional cluster frameworks. Discussion is made on varied structures and bonding which are intimately linked to the valence electron concentration, i.e., the number of electrons that held the octahedral metal cluster architecture. Exploration of the literature indicates that apart from Nb6I11 and derivatives, which show electron-deficient face-capped M6X i 8X a 6 units, compounds containing edge-bridged M6X i 12X a 6 motifs are the most largely encountered. Closed-shell compounds with a valence electron concentration of 16 are predominant, although a few 15-electron open-shell magnetic compounds or even 14-electron closed-shell species have also been reported. Particularly interesting from a structural point of view is the fashion in which these facecapped and edge-bridged clusters "pack" in crystals. The astonishing diversity of structural types, which are observed, is mainly due to the flexibility of the halogen ligands to coordinate in various manners to metal atoms. However, a rigorous structural analysis of these compounds reveals no close relationship between the valence electron concentration and the variability of the intercluster connections and/or the nature of the counter-ions. Indeed, the main bonding features of these compounds can be understood from the delocalized bonding picture of isolated 'molecular-like' M6X i 8X a 6 or M6X i 12X a 6 clusters. Keywords Crystal structure  Electronic effect  Electronic structure  Halide  Inorganic compound  Interatomic distance  Intercluster distance  Ligand  Matrix effect  Metal-metal bond  Niobium  Octahedral cluster  Structure type  Tantalum  Three-dimensional framework  Valence electron concentration Contents 5 Cluster Frameworks of Structural Formula [M6X i 12X a-a 6/2] 5.1 Cluster Compounds with Linear M-X a-aM Bridges 5.2 Cluster Compounds with Bent M-X a-aM Bridges in Cubic Structure 5.3 Cluster Compounds with Bent M-X a-aM Bridges in Trigonal Structure 5.4 Cluster Compounds with Both Linear and Bent M-X a-aM Bridges 6 Interatomic Distances in Inorganic Nb6 and Ta6 Cluster Halide Compounds with Threedimensional Frameworks 6.1 Cluster Units Based on Face-capped M6X i 8X a 6 Building Blocks 6.2 Cluster Units Based on Edge-bridged M6X i 12X a 6 Building Blocks 7 Structural Relationships Between Crystal Structures Based on Hexagonal, Cubic and Trigonal Symmetry 8 Electronic Structure of Niobium and Tantalum Octahedral Cluster Halide Compounds 8.1 Variable VEC of Nb6I11 and Derivatives 8.2 Electronic Structure of Edge-bridged M6X i 12X a 6 Clusters 9 Summary References

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“…Ta6Br15(TaBr6)0.86, formerly known as the elusive "TaBr3", was reported in 2010 by Habermehl et al [35]. This cluster compound crystallizes in the trigonal symmetry space group 3 ̅ (No.…”

Section: Ta6br15(tabr6)-typementioning

confidence: 97%

Section: Ta6br15(tabr6)-typementioning

confidence: 99%

Section: Ta6br15(tabr6)-typementioning

confidence: 99%

Section: Ta6br15(tabr6)-typementioning

confidence: 99%

See 2 more Smart Citations

Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-Dimensional Frameworks: A Review on Their Crystallographic and Electronic Structures

Lemoine

Halet

Cordier

2019

Structure and Bonding

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“…Among the reported binary phases are Hf 0.86 I 3 and TaBr 2.94 (Habermehl et al, 2010;Beekhuizen et al, 2011). Black rodshaped crystals of Hf 0.86 I 3 were produced by reducing HfI 4 with aluminum at 850 • C in the presence of NaI flux contained in a sealed tantalum vessel and held for 16 days before slow cooling to room temperature at 5 • C/h.…”

Section: Halides/oxyhalidesmentioning

confidence: 99%

“Soft” Alkali Bromide and Iodide Fluxes for Crystal Growth

et al. 2020

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In this review we discuss general trends in the use of alkali bromide and iodide (ABI) fluxes for exploratory crystal growth. The ABI fluxes are ionic solution fluxes at moderate to high temperatures, 207 to ∼1,300 • C, which offer a good degree of flexibility in the selection of the temperature profile and solubility. Although their main use is to dissolve and recrystallize "soft" species such as chalcogenides, many compositions with "hard" anions, including oxides and nitrides, have been obtained from the ABI fluxes, highlighting their unique versatility. ABI fluxes can serve to provide a reaction and crystallization medium for different types of starting materials, mostly the elemental and binary compounds. As the use of alkali halide fluxes creates an excess of the alkali cations, these fluxes are often reactive, incorporating one of its components to the final compositions, although some examples of non-reactive ABI fluxes are known.

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ChemInform Abstract: The Last of the Five: The Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta₆}Br₁₂]Br₃ [TaBr₆]_0.86.

2010

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The Last of the Five: the Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta₆}Br₁₂]Br₃[TaBr₆]_0.86

Cited by 5 publications

References 19 publications

Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-Dimensional Frameworks: A Review on Their Crystallographic and Electronic Structures

Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-Dimensional Frameworks: A Review on Their Crystallographic and Electronic Structures

“Soft” Alkali Bromide and Iodide Fluxes for Crystal Growth

ChemInform Abstract: The Last of the Five: The Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta₆}Br₁₂]Br₃ [TaBr₆]_0.86.

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The Last of the Five: the Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta6}Br12]Br3[TaBr6]0.86

Cited by 5 publications

References 19 publications

Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-Dimensional Frameworks: A Review on Their Crystallographic and Electronic Structures

Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-Dimensional Frameworks: A Review on Their Crystallographic and Electronic Structures

“Soft” Alkali Bromide and Iodide Fluxes for Crystal Growth

ChemInform Abstract: The Last of the Five: The Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta6}Br12]Br3 [TaBr6]0.86.

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The Last of the Five: the Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta₆}Br₁₂]Br₃[TaBr₆]_0.86

ChemInform Abstract: The Last of the Five: The Elusive “Tantalum(III) Bromide”, a Perovskite‐Related Salt, [{Ta₆}Br₁₂]Br₃ [TaBr₆]_0.86.