On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium and phosphorus) in ionic liquids

The chemical reactivity of phosphonium based ionic liquids (ILs) towards tellurium at temperatures above 220 °C was systematically investigated by a series of dissolution experiments, tracking the solute tellurium species by nuclear magnetic resonance, and characterizing the reaction products by X‐ray diffraction and scanning electron microscopy. The initial step is the thermal elimination of an alkyl group of the phosphonium cation of the ILs, most probably via an SN2 mechanism. The addition of tellurium follows to form trialkylphosphane tellurides as evidenced by 31P and 125Te NMR spectroscopic experiments. The trialkylphosphane tellurides can serve as a tellurium reservoir for the formation of metal tellurides, like Bi2Te3 and Ag2Te. It was observed that trihexyltetradecylphosphonium chloride ([P6 6 6 14]Cl) shows a very weak reactivity that is reflected by a low solubility of tellurium, while trihexyltetradecylphosphonium dicyanamide/decanoate ([P6 6 6 14][N(CN)2]/[P6 6 6 14][decanoate]) and tetrabutylphosphonium decanoate ([P4 4 4 4][decanoate]) dissolve tellurium to a much higher extent. We attribute these observations to the different Lewis basicity of the anions of the ILs as main influencing factor.

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“…Boros et al. found that the dilute solution of tellurium in [P 6 6 6 14 ][decanoate] shows a purple color . Ding et al.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Chemical Reactivity of Phosphonium‐Based Ionic Liquids with Tellurium

Zhang

Schwedtmann

Weigand

et al. 2018

Chemistry A European J

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“…[1] Among the many possible solvents in whicht he synthesis of phosphorus compounds from, for example, PCl 3 can be performed, ionic liquids (ILs) have remarkable potential. [15][16][17][18][19] Recently,R uck et al observed that in 1-hexyl-3-methylimidazoliumh alide ILs ([HMIm]Z;Z= Cl, Br,I )p hosphorust rihalides (PX 3 ;X= Cl, Br,I )c an readily undergo X-to-Zh alide exchange with the solvent, [20] which offersa ne fficientw ay of interconvertingt hese compounds. [2,5,14] Accordingly,s ignificants cientific attention has been devotedt oe xploring the possibility of combining the rich chemistryo fp hosphorus compounds and the versatility of IL solvents.…”

Section: Introductionmentioning

confidence: 99%

Spontaneous Substitutions at Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: Grotthuss Diffusion of Anions?

Hollóczki

Wolff

Pallmann

et al. 2018

Chemistry A European J

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PX compounds (X=Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z=Cl, Br, I) of the solvent to form [PX Z] complex anions. These anions have a sawhorse shape in which the lone pair of the phosphorus atom fills the third equatorial position of the pseudotrigonal bipyramid. Theoretical results show that this association remains incomplete due to strong hydrogen bonding with the cations of the ionic liquid, which competes with the phosphorus trihalide for interaction with the Z anion. Temperature-dependent P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiment evidence dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. Detailed knowledge of the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic-liquid mixtures.

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“…more recently reported detailed electrochemical studies of sulfur and sodium polysulfides in 1‐butyl‐3‐methylimidazolium dicyanamide . The solubility of chalcogens and phosphorus in a variety of ionic liquids comprising tosylate, bistriflimide, dithiocarbamate, and di‐ and trithiocarbonate anions was investigated by Seddon and co‐workers . The sulfur solubility in 1‐ethyl‐3‐methylimidazolium bistriflimide was also studied with the aim to electrodeposit metal sulfide films .…”

Section: Introductionmentioning

confidence: 99%

Halide‐Free Synthesis of Hydrochalcogenide Ionic Liquids of the Type [Cation][HE] (E=S, Se, Te)

Finger

2016

Chemistry A European J

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We present the synthesis and thorough characterization of ionic liquids and organic salts based on hydrochalcogenide HE(-) (E=S, Se, Te) anions. Our approach is based on halide-, metal-, and water-free decarboxylation of methylcarbonate precursors under acidic conditions, resulting from the easily dissociating reagents H2 E. The compounds were characterized by elemental analysis, multinuclear NMR spectroscopy, thermal and single-crystal XRD analyses. The hydrosulfide salts were investigated with respect to their ability to dissolve elemental sulfur in varying stoichiometry. Thus-prepared polysulfide ILs were also analyzed by UV/Vis spectroscopy and cyclic voltammetry.

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On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium and phosphorus) in ionic liquids

Cited by 80 publications

References 17 publications

Understanding the Chemical Reactivity of Phosphonium‐Based Ionic Liquids with Tellurium

Understanding the Chemical Reactivity of Phosphonium‐Based Ionic Liquids with Tellurium

Spontaneous Substitutions at Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: Grotthuss Diffusion of Anions?

Halide‐Free Synthesis of Hydrochalcogenide Ionic Liquids of the Type [Cation][HE] (E=S, Se, Te)

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