Lanthanide complexes dithiophosphates

The coordination mode of the dithiophosphate ligands and the overall geometry of the complex (shown in Fig. 2.4, bottom) match what is known in the literature. Several lanthanide dithiophosphate complexes are published in the Cambridge Structural Database (CSD) [36], and they fall in one of the three categories anionic complexes with four dithiophosphate ligands [37,38], neutral complexes with three dithiophosphate ligands and two neutral unidentate ligands [39—43], and cationic... 

The presence of coordinated chloride ions, however, is unprecedented. Most lanthanide dithiophosphate complexes are synthesized from lanthanide chloride hydrates using methods derived from one published by Pinkerton et al. [45]. In... 

The complexes expected to form when lanthanide ions are extracted into an organic solvent by a dithiophosphate extractant match those in the reported crystal structures [46]. However, [P4444][La(S2P(OEt)2)2Cl3] was crystallized directly from a reaction of LaCls 7H2O with the dithiophosphate salt and can be understood as the result of substitution of coordinated water molecules by IL ions. In this sense, the crystal stmcture should bear a closer relationship to the complexes formed when LaCls is dissolved in this IL, which differ from those expected in an organic solvent. 

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