Dimers of Heptapnictide Anions:  As144- and P144- in the Crystal Structures of [Rb(18-crown-6)]4As14·6NH3 and [Li(NH3)4]4P14·NH3

Hanauer, Tobias; Aschenbrenner, Jürgen C.; Korber, Nikolaus

doi:10.1021/ic060418j

Cited by 35 publications

(25 citation statements)

References 39 publications

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“…[23] However,consid- Figure 2. Displacementellipsoids set at 50 %p robability.S elected bond lengths []: As1-As2 2.3545(15), As1-As5 2.4355(11), As2-As6 2.4278(13), As3-As42 .3648 (14), As3-As62 .4203(13), As4-As5 2.4309- (14), As5-As72 .4523 (14),A s6-As72 .4424 (12),A s7-As82 .4434(12), As8-As13 2.4234(13), As8-As9 2.4559(11), As9-As10 2.3819(12), As10-As112 .5738 (13),A s11-As122 .3775(13), As12-As13 2.4384(12), As13-As142 .4438 (11),A s14-As152 .4737 (12), As14-As18 2.4400(11), As15-As162 .3553 (14),A s16-As172 .3696 (14), As17-As18 2.3604- (13). [28] Hydrogen atoms are omitted for clarity.Displacementellipsoids set at 50 %p robability.S elected bond lengths []a nd angles [8 8]: As1-As1' 2.4377(19), As1-As22 .4026(16), As2-As32 .4357 (14), As3-As4 2.3563- (14), As4-As52 .4294 (14),A s5-As62 .4423 (15),A s6-As72 .3648 (14), As1-As5 2.3901(15),A s2-As7 2.4380 (14);A s1-As2-As3 106.30(6), As1-As5-As4 106.77(6), As1-As5-As6 98.55(5), As1-As2-As7 99.02(5), As2-As1-As5 102.15(5), As2-As1-As1' 97.50 (7), As2-As3-As4 106.51(5), As3-As2-As7 80.60(4), As3-As4-As5 106.26(5), As4-As5-As6 81.82(5), As5-As1-As1' 97.39(6), As5-As6-As7 106.20 (5).…”

Section: Communicationsmentioning

confidence: 99%

“…[10,11] This indicates interesting behavior for this compound as ap otential As source because arsenic-rich polyarsenides in particular are rare to date.Most of them have been obtained from reactions of the Zintl ion As 7 3À with transition-metal and main-group-metal precursors (Scheme 1). [12] An outstanding example is the synthesis of [PBu 4 ] 3 [As@Ni 12 @As 20 ], which contains an icosahedral [Ni 12 (m 12 -As)] 3À core incorporated into af ullerenelike As 20 cage. [12d] In 1988, Haushalter and co-workers reported on [Rb(crypt)] 4 [As 22 ]·dmf (dmf = dimethylformamide,c rypt = 4,7,13,16,21,24-hexaoxa-1,10-diazatricyclo- [8.8.8]hexacosane), which is,t ot he best of our knowledge, the largest polyarsenide that has been reported thus far.…”

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Arsenic‐Rich Polyarsenides Stabilized by Cp*Fe Fragments

et al. 2017

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The redox chemistry of [Cp*Fe(η -As )] (1, Cp*=η -C Me ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η -P )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel As scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme) ][{Cp*Fe(μ,η -As )} ] (2) and the arsenic-rich complexes [K(dme) ] [(Cp*Fe) (μ,η -As )] (3), [K(dme) ] [(Cp*Fe) (μ,η -As )] (4), and [K(dme) ] [(Cp*Fe) (μ ,η -As )] (5). Compound 4 and the polyarsenide complex 5 are the largest anionic As ligand complexes reported thus far. Complexes 2-5 were characterized by single-crystal X-ray diffraction, H NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η -As )] , which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe) (μ,η -As )] .

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Section: Communicationsmentioning

confidence: 99%

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confidence: 99%

Arsenic‐Rich Polyarsenides Stabilized by Cp*Fe Fragments

et al. 2017

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“…The cage clusters are of interest because they are, in essence, systems of fused rings, but they form cages rather than polymeric fragments, such as layers or frame works. The adamantane like cluster P 10 6-is unique, is not present in binary phosphides, and was found only in mixed phosphides Cu 4 SnP 10 (see Ref. 2) and Au 3 SnCuP 10 .…”

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“…1 Both discrete phosphorus clusters and one , two , and three dimensional infinite fragments are known. Finite frag ments, for example, such chain anions as P 3 5-, P 4 6-, and P 5 7-, cyclic anions, for example, P 4 4-and P 6 6-, and the cage anions P 7 3-, P 10 6-, and P 11 3-belong to discrete clusters. The cage clusters are of interest because they are, in essence, systems of fused rings, but they form cages rather than polymeric fragments, such as layers or frame works.…”

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Synthesis and crystal structure of new double mercury silver phosphide iodide Hg12Ag41P88I41

et al. 2007

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New double mercury silver phosphide iodide Hg 12 Ag 41 P 88 I 41 (1) was synthesized and its crystal structure was established. Compound 1 crystallizes in the cubic system. The character istic feature of the crystal structure 1 is the presence of the anionic cage clusters P 11 3-, which have been previously found in alkali metal compounds only. The well ordered P 11 3-clusters form a system of polyhedra, which encapsulate various disordered α AgI type fragments.Key words: double mercury silver phosphide iodide, synthesis, crystal structure, phospho rus cluster, disorder, energy dispersive X ray analysis.The tendency of phosphorus to form homonuclear bonds is responsible for the existence of numerous phos phides with various stoichiometries and structures. 1 Both discrete phosphorus clusters and one , two , and three dimensional infinite fragments are known. Finite frag ments, for example, such chain anions as P 3 5-, P 4 6-, and P 5 7-, cyclic anions, for example, P 4 4-and P 6 6-, and the cage anions P 7 3-, P 10 6-, and P 11 3-belong to discrete clusters. The cage clusters are of interest because they are, in essence, systems of fused rings, but they form cages rather than polymeric fragments, such as layers or frame works. The adamantane like cluster P 10 6-is unique, is not present in binary phosphides, and was found only in mixed phosphides Cu 4 SnP 10 (see Ref. 2) and Au 3 SnCuP 10 . 3 The most abundant are the P 7 3-clusters, which were found in phosphides with the compositions M 3 P 7 (for alkali metals) 1,4,5 and M 3 P 14 (for Sr and Ba) 6,7 and in the Ba 2 P 7 Cl compound. 8 Oligomeric and polymeric moieties based on the P 7 3-cage clusters were also documented. 1,9,10 The P 11 3-cage clusters do not form polymeric fragments and were found only in alkali metal compounds, for ex ample, in phosphides with the composition M 3 P 11 . 1,11,12 Compounds, in which the P 11 3-clusters are stabilized by the coordination of alkali metal atoms to large organic ligands, which prevent the phosphorus atoms from inter acting directly with alkali metal atoms and forming sim pler structures, were also documented. The Cs 3 (en) 3 P 11 compound 13 can be given as an example of such com pounds.In the present study, we report the synthesis and the crystal structure of new double mercury silver phosphide iodide Hg 12 Ag 41 P 88 I 41 (1), which is the first example of the presence of the phosphorus cluster P 11 3-in com pounds containing no alkali metals. Results and DiscussionCompound 1 is dark red in color and is stable to atmo spheric moisture. It was synthesized by the conventional ampoule techniques. To optimize the conditions of the preparation of a single phase sample, we varied the an nealing temperature (400-650 °C) and the duration of heating (0.5-24 h) and cooling (quenching, the switched off furnace mode, 5 deg h -1 ) and used different starting reagents (HgI 2 , Hg 2 I 2 , AgI, Hg, Ag, and P). A single phase sample was prepared by rapid heating of a mixture with the composition 41AgI : 12Hg : 88P to 500 °C and a...

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“…Therefore, they can be considered as a subclass of intermetalloid clusters. The accessibility of larger intermetalloid 124 T.F. F€ assler clusters via deltahedral homoatomic Zintl ions may be very useful for syntheses in the field of materials science, and finally, the recent discovery of the first siliconcontaining Zintl ions that can serve as building blocks for larger cluster units has provided another promising aspect, since silicon-based materials will have an even larger impact than, e.g., germanium-based materials.…”

Section: Summary and Concluding Remarksmentioning

confidence: 99%

Relationships Between Soluble Zintl Anions, Ligand-Stabilized Cage Compounds, and Intermetalloid Clusters of Tetrel (Si–Pb) and Pentel (P–Bi) Elements

Fässler

2011

Structure and Bonding

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The high abundance of nine-and seven-or eleven-atom clusters of group 14 and group 15 elements, respectively, led to an enhanced investigation of the versatile chemical reactivity of these species. The studies showed that these clusters are ideal precursors for the synthesis of larger units, functionalized cage molecules, and endohedrally filled clusters. They can further serve as building blocks for large homoatomic and heteroatomic intermetalloid clusters as well as for nanostructured materials. In this chapter, the chemistry and the structures of Zintl ions and their derivatives and of cage molecules are summarized and put in the context of intermetalloid clusters. The emphasis is put on the fact that irrespective of the starting material (Zintl ions or small low-valent organometallic compounds), the same types of intermetalloid clusters are formed, and the similarities of ligandcarrying metalloid clusters and intermetalloid anions that arise from reactions of soluble Zintl ions will be pointed out.

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Dimers of Heptapnictide Anions: As₁₄⁴^- and P₁₄⁴^- in the Crystal Structures of [Rb(18-crown-6)]₄As₁₄·6NH₃ and [Li(NH₃)₄]₄P₁₄·NH₃

Cited by 35 publications

References 39 publications

Arsenic‐Rich Polyarsenides Stabilized by Cp*Fe Fragments

Arsenic‐Rich Polyarsenides Stabilized by Cp*Fe Fragments

Synthesis and crystal structure of new double mercury silver phosphide iodide Hg12Ag41P88I41

Relationships Between Soluble Zintl Anions, Ligand-Stabilized Cage Compounds, and Intermetalloid Clusters of Tetrel (Si–Pb) and Pentel (P–Bi) Elements

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