Document Type

Article

Publication Version

Published Version

Publication Date

2013

Journal or Book Title

Inorganic Chemistry

Volume

52

Issue

24

First Page

13997

Last Page

14009

DOI

10.1021/ic401676r

Abstract

The system trihexyl(tetradecyl)phosphonium ([P66614]Cl)/mercury chloride (HgCl2) has been investigated by varying the stoichiometric ratios from 4:1 to 1:2 (25, 50, 75, 100, 150, and 200 mol % HgCl2). All investigated compositions turn out to give rise to ionic liquids (ILs) at room temperature. The prepared ionic liquids offer the possibility to study the structurally and compositionally versatile chloromercurates in a liquid state at low temperatures in the absence of solvents. [P66614]2[HgCl4] is a simple IL with one discrete type of anion, while [P66614]{HgCl3} (with {} indicating a polynuclear arrangement) is an ionic liquid with a variety of polyanionic species, with [Hg2Cl6]2– apparently being the predominant building block. [P66614]2[Hg3Cl8] and [P66614][Hg2Cl5] appear to be ILs at ambient conditions but lose HgCl2 when heated in a vacuum. For the liquids with the compositions 4:1 and 4:3, more than two discrete ions can be evidenced, namely, [P66614]+, [HgCl4]2–, and Cl– and [P66614]+, [HgCl4]2–, and the polynuclear {HgCl3}−, respectively. The different stoichiometric compositions were characterized by 199Hg NMR, Raman- and UV–vis spectroscopy, and cyclic voltammetry, among other techniques, and their densities and viscosities were determined. The [P66614]Cl/HgCl2 system shows similarities to the well-known chloroaluminate ILs (e.g., decrease in viscosity with increasing metal content after addition of more than 0.5 mol of HgCl2/mol [P66614]Cl, increasing density with increasing metal content, and the likely formation of polynuclear/polymeric/polyanionic species) but offer the advantage that they are air and water stable.

Comments

Reprinted with permission from Inorg. Chem., 2013, 52 (24), pp 13997–14009. Copyright (2013) American Chemical Society

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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