Mercury scrubbing from gas streams using a supported 1-butyl-3-methylimidazolium chlorocuprate(ii) ionic liquid ([Cmim][CuCl]) has been studied using operando EXAFS. Initial oxidative capture as [HgCl] anions was confirmed, this was then followed by the unanticipated generation of mercury(i) chloride through comproportionation with additional mercury from the gas stream. Combining these two mechanisms leads to net one electron oxidative extraction of mercury from the gas with increased potential capacity and efficiency for supported ionic liquid mercury scrubbers.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2015
The first examples of ionic liquids based on borenium cations, [BCl2 L](+), are reported. These compounds form highly Lewis acidic liquids under solvent-free conditions. Their acidity was quantified by determining the Gutmann acceptor number (AN).
View Article and Find Full Text PDFThe liquid structure of pyridine-acetic acid mixtures have been investigated using neutron scattering at various mole fractions of acetic acid, χHOAc = 0.33, 0.50, and 0.
View Article and Find Full Text PDFPhys Chem Chem Phys
November 2014
Gutmann Acceptor Number (AN) values have been determined for Brønsted acid-ionic liquid mixtures, over a wide compositional range. Four systems of general formula [C2mim][A]-HA (A(-) = bistriflamide, [NTf2](-); triflate, [OTf](-); mesylate, [OMs](-); or acetate, [OAc](-), [C2mim](+) = 1-ethyl-3-methylimidazolium cation) were studied. A library of Brønsted acidic systems of varying acidity was constructed and the AN parameter was found to be a convenient approach for quantifying their acidity.
View Article and Find Full Text PDFA range of chloroplumbate(II) organic salts, based on the two cations, 1-ethyl-3-methylimidazolium and trihexyl(tetradecyl)phosphonium, was prepared by ionothermal synthesis. Depending on the structure of the organic cation and on the molar ratio of PbCl2 in the product, χPbCl2, the salts were room-temperature ionic liquids or crystalline organic/inorganic hybrid materials. The solids were studied using Raman spectroscopy; the crystal structure of [C2mim]{PbCl3} was determined and shown to contain 1D infinite chloroplumbate(II) strands formed by edge-sharing tetragonal pyramids of pentacoordinate (PbCl5) units.
View Article and Find Full Text PDFThe reactions of bis(mercaptoimidazolyl)hydroborato derivatives [Bm(R)]M' (R = Me, Bu(t); M' = Li, Na, Tl) with MX(3) trihalides of aluminium, gallium and indium yield both 1:1 and 2:1 complexes of the types [Bm(R)]MX(2) and [Bm(R)](2)MX, respectively. Structurally characterized examples of the [Bm(R)]MX(2) series include [Bm(Me)]AlCl(2), [Bm(Me)]GaI(2), [Bm(Me)]InI(2), [Bm(Bu(t))]AlCl(2) and [Bm(Bu(t))]GaX(2) (X = Cl, Br, I), while structurally characterized examples of the [Bm(R)](2)MX series include [Bm(Bu(t))](2)InX (X = Cl, Br, I). In addition to the halide complexes, the trivalent dimethyl thallium complex [Bm(Bu(t))]TlMe(2) has been synthesized via the reaction of [Bm(Bu(t))]Tl with Me(2)TlCl.
View Article and Find Full Text PDFThe effects of a series of Ga(III) complexes with tripodal ligands on the hydrolysis rate of the activated phosphate diester bis(2,4-dinitrophenyl)phosphate (BDNPP) have been investigated. In particular, the influence of the nature of the ligand donor sites on the reactivity of Ga(III) which represents a mimic of the Fe(III) ion in purple acid phosphatase has been evaluated. It has been shown that replacing neutral nitrogen donor atoms and carboxylate groups by phenolate groups enhanced the reactivity of the Ga complexes.
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