M. Drew, L. Glaves, M. Hudson
1985
Citations
0
Influential Citations
5
Citations
Journal
Journal of The Chemical Society-dalton Transactions
Abstract
2-Nonylpyridine 1-oxide (npyo) is a versatile solvent-extraction reagent when dissolved in chloroform. Adjustment of the acid strength (HCl) and reagent concentration can be used to bring about a range of separations. For example, npyo is effective at separating the [AuCl4]– ion from other chloro-anions of the platinum-group metals. If required, the [FeCl4]– anion may be coextracted at high acid concentration (6 mol dm–3 HCl). Chloro-anions of PtIV can be 90% extracted at npyo concentrations greater than 0.2 mol dm–3 in chloroform in a single batch operation. Chloro-anions of IrIV and RhIII may also be separated. The crystal structure of [H(npyo)2][AuCl4] indicates that there are discrete [AuCl4]– ions with weak O ⋯ Au interactions. Crystals are triclinic, space group P, Z= 4, with a= 17.351(11), b= 10.381(9), c= 20.373(8)A, α= 88.5(1), β= 101.8(1), and γ= 99.6(1)°. 4 846 Independent data above background [I > 3σ(I)] were collected on a diffractometer and the structure refined to R 0.0585. The structure contains two independent [H(npyo)2]+ cations and one [AuCl4]– in general positions and two [AuCl4]– ions in special positions with the gold atoms on centres of symmetry. Each [H (npyo)2]+ cation consists of pairs of npyo ligands associated via a hydrogen atom [O ⋯ O 2.412(19) and 2.391(16)A]. The [AuCl4]– anions are square planar but two oxygen atoms approach one of the gold atoms in axial positions [3.544(16) and 3.263(15)A], to provide some weak interaction which may provide a clue to the effectiveness of npyo in the extraction of [AuCl4]–.