Liquid silver tris(perfluoroethyl)trifluorophosphate salts as new media for propene/propane separation

Pliquett, Daniel; Schulz, P.; Heinemann, Frank W.; Bause, Angela; Wasserscheid, Peter

doi:10.1039/c6cp05653a

Cited by 8 publications

(12 citation statements)

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“…1.924(2), 1.933(2) for 1a [43a] and 1.932(8), 1.911(8) for 1b [42c] ). The structure reveals the presence of the mer-isomer of the FAP anion in agreement with the 19 FNMR spectrumi ns olution, which shows only the signals of this isomer.T he solid-state structures of the metal complexespresented previously by Mochida and Kimata [39] and Wasserscheid et al [38] as well as the fluorophosphonium salt reported by Hoge et al [36] also contain the mer-isomero ft he FAP anion.…”

Section: Nickel Complexesmentioning

confidence: 66%

“…Wasserscheid et al obtained as eries of silver salts by metathesis using AgNO 3 and KFAP in different solvents and investigated propene/propane separation using these salts. [38] The complexes [Co(h 5 -C 5 H 5 ) 2 ]FAP and [Ru(h 5 -C 5 H 5 )(h 6 -C 6 H 6 )]FAP have been prepared by anion exchange of the parentm etal chloridecomplexes with NaFAP. [39] Surprisingly,f luoridea bstraction from transition metal fluoride complexes by tris(pentafluoroethyl)difluorophosphorane is unexplored.…”

Section: Introductionmentioning

confidence: 99%

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Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Föhrenbacher

Krahfuß

Zapf

et al. 2021

Chemistry A European J

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Fluoride abstraction from different types of transition metal fluoride complexes [LnMF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C2F5)3PF2 to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2F5)3PF3]−) is reported. (C2F5)3PF2 reacted with trans‐[Ni(iPr2Im)2(ArF)F] (iPr2Im=1,3‐diisopropylimidazolin‐2‐ylidene; ArF=C6F5, 1 a; 4‐CF3‐C6F4, 1 b; 4‐C6F5‐C6F4, 1 c) through fluoride transfer to form the complex salts trans‐[Ni(iPr2Im)2(solv)(ArF)]FAP (2 a‐c[solv]; solv=Et2O, CH2Cl2, THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh3, solvent coordination was suppressed and the complexes trans‐[Ni(iPr2Im)2(PPh3)(C6F5)]FAP (trans‐2 a[PPh3]) and cis‐[Ni(iPr2Im)2(Dipp2Im)(C6F5)]FAP (cis‐2 a[Dipp2Im]) (Dipp2Im=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) were isolated. Fluoride abstraction from [(Dipp2Im)CuF] (3) in CH2Cl2 or 1,2‐difluorobenzene led to the isolation of [{(Dipp2Im)Cu}2]2+2 FAP− (4). Subsequent reaction of 4 with PPh3 and different carbenes resulted in the complexes [(Dipp2Im)Cu(LB)]FAP (5 a–e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp2Im)Cu(C6Me6)]FAP (5 f), which serves as a source of [(Dipp2Im)Cu)]+. Fluoride abstraction of [Cp2TiF2] (7) resulted in the formation of dinuclear [FCp2Ti(μ‐F)TiCp2F]FAP (8) (Cp=η5‐C5H5) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.

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Section: Nickel Complexesmentioning

confidence: 66%

Section: Introductionmentioning

confidence: 99%

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Föhrenbacher

Krahfuß

Zapf

et al. 2021

Chemistry A European J

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“…Silver salts are known to form π‐complexes with olefins, which makes them interesting in processes concerning the gas separation of mixtures of alkenes and alkanes . Recently, the silver salts [Ag(CH 3 CN) x ][P(C 2 F 5 ) 3 F 3 ] ( x= 2, 4) have been successfully applied in experiments for the separation of alkenes and alkanes . In order to investigate the gas separation capability of 1 g , we first conducted a blind test and stirred neat 1 g for 30 minutes in an atmosphere of a butane/propane mixture (85:15), without any detectable uptake of the gas.…”

Section: Resultsmentioning

confidence: 99%

“…[29] Recently,t he silver salts [Ag(CH 3 CN) x ][P(C 2 F 5 ) 3 F 3 ]( x = 2, 4) have been successfully applied in experiments fort he separation of alkenes and alkanes. [30] In order to investigate the gas separation capability of 1g,w ef irst conducted ab lind test and stirred neat 1g for 30 minutes in an atmosphere of ab utane/propane mixture (85:15), withouta ny detectable uptake of the gas. The treatment of 1g with isobutene during45minutes at room temperature, however, resulted in an absorption of isobutenea nd a liquefaction of the viscouss alt.…”

Section: Resultsmentioning

confidence: 99%

Activation of Acetonitrile with (C₂F₅)₃PF₂ and Amines

Bader

Neumann

Stammler

et al. 2018

Chemistry A European J

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Acetonitrile is deprotonated by a combination of the strong Lewis acid (C F ) PF and triethylamine. The resulting cyanomethyl function is bound to the phosphorus moiety, affording the highly stable salt [HNEt ][P(C F ) F (CH CN)]. Salt metathesis reactions furnished the corresponding [Cu(MeCN) ] and [Ag(MeCN)] derivatives in which the CH CN substituent of the anion [P(C F ) F (CH CN)] coordinates to the metal. An investigation of the gas separation capability of the silver salt [Ag(MeCN)][P(C F ) F (CH CN)] shows an uptake of 1.7 equivalents of isobutene from a propane/isobutene mixture. The reaction of (C F ) PF with acetonitrile and diethylamine furnishes [P(C F ) F {NHC(CH )NEt }]-a phosphate featuring an amidine ligand which formally results from hydroamination of acetonitrile by HNEt . Exchange of HNEt with the primary amines H NPh and H NBu leads to comparable amidine salts that exhibit a solvent-dependent conformational isomerism.

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“…65 2) Å correspondingly. 71 Luminescence Properties. The design of transition-metal complexes or clusters with long-lived excited states and high emission quantum yields is a highly important task for modern coordination chemistry.…”

Section: ■ Introductionmentioning

confidence: 99%

Self-Assembly of Ag⁺/[PW₁₁NbO₄₀]^4– Complexes in Nonaqueous Solutions

et al. 2020

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Self-assembly between Ag+ and [PW11NbO40]4– in N- and O-donor solvents (nitriles and amides) has been studied. In the case of dimethylformamide (DMF), formation of a yellow [Ag4(DMF)12][PW11NbO40] (1a) metastable phase and a colorless [Ag4(DMF)10][PW11NbO40] (1) stable phase was observed. In acetonitrile (CH3CN), the product was [Ag(CH3CN)4]2{[Ag(CH3CN)3]2[PW11NbO40]} (2a). By contrast, [SiW12O40]4– of the same size and charge as [PW11NbO40]4– produces [Ag(CH3CN)3]4[SiW12O40] (3a). Partial desolvation of 2a and 3a leads to Ag4[PW11NbO40]·7.5CH3CN (2) and Ag4[SiW12O40]·7.5CH3CN (3), respectively. The CH3CN molecules in the structure of 2 are labile, and this compound was used as the starting material to study solvent-exchange processes in N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMA), diethylformamide (DEF), and benzonitrile (PhCN) solutions. These solvent reactions yield [Ag(DMA)4][Ag3(DMA)6][PW11NbO40] (4), [Ag2(NMP)4(CH3CN)]2[PW11NbO40]·1.3NMP (5a), [Ag2(NMP)5]2[PW11NbO40] (5b), Ag4[PW11NbO40]·9.5DEF (6), and [Ag(PhCN)4]2[{Ag(PhCN)3}2PW11NbO40] (7). All products were isolated and characterized by single-crystal X-ray diffraction (except for 2 and 3), IR, elemental analysis, and thermogravimetric analysis techniques. The O-donor solvents favor polynuclear, solvent-bridged cationic aggregates. In the case of DMF, DMA, and DEF discrete, tri- and tetranuclear polycations are observed, while in the case of NMP, the formation of infinite polycationic structures takes place. By contrast, the N-donor solvents (CH3CN and PhCN) favor mononuclear cations, which can exist either as distorted tetrahedral, isolated [Ag(Solv)4]+ cations or as pseudotriangular {Ag(Solv)3}+ units, additionally coordinated to a polyoxometalate. Screening of the luminescent properties for solid samples of 1–7 revealed that only 5a/5b and 7 are emissive. In particular, the sample containing 5a and 5b demonstrates long-lived phosphorescence with a 30 ms lifetime.

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Liquid silver tris(perfluoroethyl)trifluorophosphate salts as new media for propene/propane separation

Cited by 8 publications

References 50 publications

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Activation of Acetonitrile with (C₂F₅)₃PF₂ and Amines

Self-Assembly of Ag⁺/[PW₁₁NbO₄₀]^4– Complexes in Nonaqueous Solutions

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Liquid silver tris(perfluoroethyl)trifluorophosphate salts as new media for propene/propane separation

Cited by 8 publications

References 50 publications

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Activation of Acetonitrile with (C2F5)3PF2 and Amines

Self-Assembly of Ag+/[PW11NbO40]4– Complexes in Nonaqueous Solutions

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Product

Resources

About

Activation of Acetonitrile with (C₂F₅)₃PF₂ and Amines

Self-Assembly of Ag⁺/[PW₁₁NbO₄₀]^4– Complexes in Nonaqueous Solutions