Lewis Acid Catalyzed Synthesis of Cyanidophosphates

Bläsing, Kevin; Ellinger, Stefan; Harloff, Jörg; Schulz, Andreas S.; Sievert, Katharina; Täschler, Christoph; Villinger, Alexander; Täschler, Cornelia Zur

doi:10.1002/chem.201504523

Cited by 14 publications

(12 citation statements)

References 49 publications

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“…Ternary pnictogen(V) cyanides are not known to date. Only recently, the isolation and full characterization of salts containing the fluorido‐cyanido phosphate anions of the type [PF 6‐ n (CN) n ] − (with n =1–5) were achieved …”

Section: Methodsmentioning

confidence: 99%

Molecular E(CN)₃ (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Arlt

Harloff

Schulz

et al. 2016

Chemistry A European J

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The heavy pnictogen tricyanides, E(CN) (E=Sb, Bi), were synthesized from EF and Me SiCN in ionic liquids, for example, 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIm][OTf]), which prevents the oligomerization of the molecular E(CN) species by formation of [BMIm][E(CN) (OTf)] salts in solution. Recrystallization of [BMIm][E(CN) (OTf)] from THF led to the isolation and full characterization of the molecular species E(CN) ⋅2 THF.

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Section: Methodsmentioning

confidence: 99%

Molecular E(CN)₃ (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Arlt

Harloff

Schulz

et al. 2016

Chemistry A European J

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“…Nur einige Strukturberechnungen wurden bislang veröffentlicht . Es hat sich gezeigt, dass Me 3 Si‐CN ein besonders wertvolles Reagens für Fluorido/Cyanido‐Austauschreaktionen ist, wie am Beispiel der Synthese von Cyanidoboraten ([B(CN) 4− n F n ] − , n =0–3) sowie ‐phosphaten ([P(CN) 6− n F n ] − , n =1–5) gezeigt wurde. Diese Reaktionen sind thermodynamisch begünstigt, da Fluortrimethylsilan (Me 3 Si‐F), das eine starke Si‐F‐Bindung mit einer hohen Bindungsdissoziationsenergie aufweist [(576±17) kJ mol −1 ], gebildet wird.…”

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“…Zusätzlich kann das Gleichgewicht der Austauschreaktion entweder durch Verwendung von Me 3 Si‐CN in großem Überschuss oder durch Abdestillieren des Me 3 Si‐F unter Standardbedingungen (Siedepunkt 16.0 °C) beeinflusst werden. Es wurde auch gezeigt, dass Lewis‐Säuren wie GaCl 3 die F − /CN − ‐Austauschreaktionen signifikant beschleunigen und auch niedrigere Temperaturen ermöglichen . Über pentakoordinierte Silikatmonoanionen, die Cyanido‐Liganden enthalten, ist nur wenig bekannt .…”

Section: Figureunclassified

“…Bei zweistündiger Reaktionsführung bei 25 °C isolierten wir stets Salze, die das [SiF(CN) 5 ] 2− ‐Ion (neben Spuren von Hexacyanidosilikat [Si(CN) 6 ] 2− ) in moderaten Ausbeuten enthielten (50–60 %). Bei einer Temperaturerhöhung auf 100 °C führte die Reaktion jedoch ausschließlich zur Bildung von [Si(CN) 6 ] 2− ‐Salzen in sehr guten Ausbeuten (60–90 %) bei einer Reaktionszeit von 2 h. Mit kleinen Mengen GaCl 3 als Lewis‐Säure‐Katalysator, die dem Reaktionsgemisch zugesetzt wurden, konnte die Reaktionszeit verkürzt werden . Außerdem wurden signifikant weniger Spuren an [SiF(CN) 5 ] 2− ‐Ionen nachgewiesen.…”

Section: Figureunclassified

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Cyanidosilikate – Synthese und Struktur

et al. 2019

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Ausgehend von Fluoridosilikat-Vorstufen in reinem Cyantrimethylsilan, Me 3 Si-CN,w urde eine Reihe verschiedener Ammoniumsalze[ R 3 NMe] + (R = Et, n Pr, n Bu) mit den neuen [SiF(CN) 5 ] 2À -und [Si(CN) 6 ] 2À -Dianionen in einfachen, temperaturgesteuerten F À /CN À -Austauschreaktionen synthetisiert. Mit zersetzbaren, nicht-unschuldigen Kationen wie [R 3 NH] + konnten Metallsalzed es Typs M 2 [Si(CN) 6 ]( M + = Li + ,K + )d urchN eutralisationsreaktionen mit entsprechenden Metallhydroxiden hergestellt werden. Die ionische Flüssigkeit [BMIm] 2 [Si(CN) 6 ]( Schmp. = 72 8 8C) wurde durch eine Salzmetathesereaktion erhalten. Alle synthetisierten Salzekonnten in guten Ausbeuten isoliert und vollständig charakterisiert werden.

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“…Following our interests in pseudohalide chemistry, we focused on the synthesis of small molecules with the primary goal to make very simple isolable compounds. During the first funding period we were able to synthesize and characterize salts bearing new heteroleptic cyanido(fluorido)phosphate anions of the general formula [PF 6− n (CN) n ] − ( n =1−4), [117,118] as well as the homoleptic tetracyanidoborate anion [B(CN) 4 ] − , [119] by very mild Lewis‐acid catalyzed synthesis protocols, when starting from ILs. We succeeded in the synthesis and structural characterization of molecular pnictogen tricyanides E(CN) 3 (E=Sb, Bi), which were stabilized in the IL [BMIm][OTf] ([BMIm]=1‐ n Butyl‐3‐methylimidazolium, [OTf]=F 3 CSO 2 O − ), thus preventing these species from oligomerization [120] .…”

Section: Introductionmentioning

confidence: 99%

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

et al. 2020

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Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non‐innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT‐IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ‐nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa‐substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non‐innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained.

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Lewis Acid Catalyzed Synthesis of Cyanidophosphates

Cited by 14 publications

References 49 publications

Molecular E(CN)₃ (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Molecular E(CN)₃ (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Cyanidosilikate – Synthese und Struktur

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

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Lewis Acid Catalyzed Synthesis of Cyanidophosphates

Cited by 14 publications

References 49 publications

Molecular E(CN)3 (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Molecular E(CN)3 (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Cyanidosilikate – Synthese und Struktur

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

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Molecular E(CN)₃ (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

Molecular E(CN)₃ (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates