Asymmetrisch substituierte Iminiumsalze [Et3PNAsPh3]X und ihre Reaktion mit Acetonitril. Kristallstrukturen von [Et3PNAsPh3]X (X = Cl, Br), [(Ph3As)2CCN]Br und [(Ph3As)2CCN(SnBr5)]

Chitsaz, Soheila; Neumüller, Bernhard; Harms, Klaus; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199808)624:8<1341::aid-zaac1341>3.0.co;2-v

Cited by 16 publications

(4 citation statements)

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“…Die IR-Spektren von 1 und 2 werden durch die Banden des Kations dominiert; sie zeigen keine Auffälligkeiten gegenüber dem Spektrum von [Et 3 PNAsPh 3 ]Br [1]. Im Einklang mit der kristallographisch ermittelten hohen Symmetrie der Anionen [Ag 2 Br 4 …”

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Die Kristallstrukturen von [Et3PNAsPh3]2[Ag2Br4] und [Et3PNAsPh3]2[Pd2Br6]

Neumüller

Chitsaz

Dehnicke

2002

Z. anorg. allg. Chem.

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Colourless single crystals of [Et 3 PNAsPh 3 ] 2 [Ag 2 Br 4 ] (1) and red single crystals of [Et 3 PNAsPh 3 ] 2 [Pd 2 Br 6 ] (2) have been isolated from saturated solutions in acetonitrile of equivalent mixtures of [Et 3 PNAsPh 3 ]Br with AgBr and PdBr 2 , respectively. Both complexes were characterized by IR spectroscopy and by crystal structure determinations. 1: Space group P1, Z ϭ 1, lattice dimensions at Ϫ70°C: a ϭ 985.0(2), b ϭ 1042.2(5), c ϭ 1345.8(5) pm, α ϭ 102.88(2)°, β ϭ 105.73(2)°, γ ϭ 94.94(2)°, R 1 ϭ 0.0577. Wir berichteten unlängst über Synthese und Kristallstrukturen der asymmetrischen Phospha-Arsaiminium-Salze [Et 3 PNAsPh 3 ]X mit X ϭ Cl und Br, die durch Reaktion von Me 3 SiNPEt 3 mit Ph 3 AsX 2 leicht zugänglich sind [1]. Kationen dieses Typs, zu denen auch das [Et 3 PNPPh 3 ] ϩ [2] gehört, lassen gegenüber den symmetrischen Iminium-Salzen, wie dem häufig angewandten [Ph 3 PNPPh 3 ] ϩ oder dem seltener eingesetzen Methyl-Derivat [Me 3 PNPMe 3 ] ϩ [3] wie auch gegenüber den Arsa-Analogen [R 3 AsNPR 3 ] ϩ mit R ϭ Methyl [4] und Phenyl [5] einige Vorteile erwarten. Hierzu gehören eine größere Anpassungsfähigkeit an verschiedene Lösungsmittel, sehr gute Kristallisationseigenschaften, erweiterte Möglichkeiten bei der Konstruktion komplexer Anionen, eine unkomplizierte Syntheseroute und Hilfe bei der kristallographischen Strukturlösung. Wir berichten hier über die Kristallstrukturen von [Et 3 PNAs-Ph 3 ] 2 [Ag 2 Br 4 ] (1) und [Et 3 PNAsPh 3 ] 2 [Pd 2 Br 6 ] (2), die sich als farblose (1) und rote (2) Einkristalle aus Acetonitril-Lösungen der Komponenten gemäß Gleichungen (1, 2) bilden.

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Die Kristallstrukturen von [Et3PNAsPh3]2[Ag2Br4] und [Et3PNAsPh3]2[Pd2Br6]

Neumüller

Chitsaz

Dehnicke

2002

Z. anorg. allg. Chem.

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“…[SMe 3 ][SnBr 5 (MeCN)], see Figure , crystallizes in the space group P 2 1 / n with a C 4 v symmetry around the Sn atom and has similarities to the structures of [(Ph 3 As) 2 CCN(SnBr 5 )] and the chlorinated isomorph [S 5 N 5 ][SnCl 5 (MeCN)] . The Sn–Br bond distances vary between 253.7(1) and 258.8(1) pm.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Crystallization, and Electrochemical Characterization of Room Temperature Ionic Liquid Bromidostannates(II/IV)

et al. 2021

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Ionic liquids (IL) are valuable in a variety of applications due to their high electrochemical stability and physical properties. Using the cation 1-methyl-3-octylimidazolium, [OMIM] + , the bromidostannate RTIL [OMIM][Sn +II Br 3 ], "undercooled melt" [OMIM][Sn +IV Br 5 ], and IL [OMIM] 2 [Sn +IV Br 6 ] were synthesized. The uncommon solid state structure of [SnBr 5 ] − was elucidated in the form of its RTIL salt. Additionally, the IL based on tribromine-monoanion [OMIM][Br 3 ] was used to dissolve metallic Sn, selectively resulting in the formation of [SnBr 3 ] − as confirmed by Raman spectroscopy. Subsequent cyclic voltammograms (CV) of [SnBr 3 ] − confirmed the deposition potential of metallic Sn and renewal of the polybromide [Br 3 ] − . The RTIL bromidostannates were stable compounds, making a selective electrochemical investigation of the deposition of metallic Sn(0) to Sn(+II)/Sn(+IV) redox process possible, via conductance and CV measurements. The CVs of the RTILs and of solutions in propylene carbonate had the redox couples of Sn(0)/

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“…This compound has been reported in literature by a different route. 20 We surmise in this case that acetonitrile coordinates to the oxidized arsenic centres, rendering the hydrogen atoms more acidic, resulting in deprotonation by pyridine and eventual rearrangement to the observed product. It should be noted here that the As analogue of 3 is not known and may not be stable as it is for Bi and Sb.…”

Section: Introductionmentioning

confidence: 97%