Selective Solvent Extraction of Silver(i) by Tris-Pyridyl Tripodal Ligands and X-Ray Structure of a Silver(i) Coordination Polymer Incorporating One Such Ligand
David J. Bray A , Jack K. Clegg B , Marco Wenzel C , Kerstin Gloe C , John C. McMurtrie D , Katrina A. Jolliffe A , Karsten Gloe C and Leonard F. Lindoy A EA School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.
B School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.
C Department of Chemistry and Food Chemistry, TU Dresden, 01062 Dresden, Germany.
D School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, Qld 4001, Australia.
E Corresponding author. Email: len.lindoy@sydney.edu.au
Australian Journal of Chemistry 68(4) 549-554 https://doi.org/10.1071/CH14540
Submitted: 1 September 2014 Accepted: 23 September 2014 Published: 5 November 2014
Abstract
Two tripodal ligands, each derived from 1,1,1-tris(hydroxymethyl)ethane and terminated respectively by 4-pyridyl (L1) and 2-pyridyl groups (L2), have been synthesised. Competitive seven-metal extraction studies (H2O/CHCl3) incorporating equal concentrations of cobalt(ii), nickel(ii), copper(ii), zinc(ii), silver(i), cadmium(ii), and lead(ii) in the aqueous phase and L1 or L2 in the organic phase showed selective extraction of silver(i) in each case. A parallel solvent extraction experiment involving a related tripodal tris-pyridyl ligand (L3) based on a 1,3,5-substituted aryl ring scaffold and incorporating thioether sulfurs in each tripod arm also showed extraction selectivity for silver(i); extraction efficiencies towards this metal ion fall in the order L3 > L1 > L2. Physical data are in accord with L1 forming a capsule-like complex of type [Ag3L12]3+ in which silver ions link pairs of pyridyl groups from different ligands. In contrast, L2 yields a complex of type [Ag2L2(NO)3]n whose X-ray structure showed it to be a two-dimensional coordination polymer in which the three pyridyl donors of each L2 coordinate to three silver(i) centres, two of which are crystallographically distinct, with the centres also bonded to bidentate and/or bridging bidentate nitrato groups.
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