Issue 14, 2013

Lead(ii) chloride ionic liquids and organic/inorganic hybrid materials – a study of chloroplumbate(ii) speciation

Abstract

A 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. The liquids were analysed using 207Pb NMR and Raman spectroscopies, as well as viscometry. Phase diagrams were constructed based on differential scanning calorimetry (DSC) measurements. Discrete anions: [PbCl4]2− and [PbCl3], were detected in the liquid state. The trichloroplumbate(II) anion was shown to have a flexible structure due to the presence of a stereochemically-active lone pair. The relationship between the liquid phase anionic speciation and the structure of the corresponding crystalline products of ionothermal syntheses was discussed, and the data were compared with analogous tin(II) systems.

Graphical abstract: Lead(ii) chloride ionic liquids and organic/inorganic hybrid materials – a study of chloroplumbate(ii) speciation

Supplementary files

Article information

Article type
Paper
Submitted
16 Nov 2012
Accepted
16 Jan 2013
First published
17 Jan 2013
This article is Open Access
Creative Commons BY license

Dalton Trans., 2013,42, 5025-5035

Lead(II) chloride ionic liquids and organic/inorganic hybrid materials – a study of chloroplumbate(II) speciation

F. Coleman, G. Feng, R. W. Murphy, P. Nockemann, K. R. Seddon and M. Swadźba-Kwaśny, Dalton Trans., 2013, 42, 5025 DOI: 10.1039/C3DT32742F

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