Synthesis, Characterization, and Crystal Structures of Novel Coordination Polymers of Praseodymium(III) and Neodymium(III) Containing Dialkyl Phosphate

Abstract

Metal complexes incorporating various types of phosphate moieties are being examined in order to explore the metalbinding properties of such ligands and to elucidate the importance of these interactions in biological systems. Mononuclear, 37 In this complex, DMP is not bonded to the metal, and acts as a independent counter-ion. We have also reported the synthesis and crystal structures of [Fe 16 38 within which an macromolecule constellation consisting of sixteen iron ion connected by twelve bridging dimethyl phosphate, twelve bridging acetate, eight µ3-oxo, four µ3-OH, four µ-OH and four dimethyl sulfoxide ligands. We now report on the synthesis, characterization and crystal structure of novel polymer of praseodymium(III) and neodymium(III) complexes. Experimental SectionAll chemicals were purchased from Merck and Aldrich. Infrared spectra (4000-250 cm -1 ) of solid samples were taken as 1% dispersion in KBr pellets using a Shimadzu-470 spectrometer. H NMR, 13C NMR and 31 P NMR spectra were acquired on a Bruker AC-300 MHz spectrometer at ambient temperature in D2O. Melting points were is uncorrected and were obtained by a Kofler Heizbank Rechart type 7841 melting point apparatus.Synthesis of [Nd(µ-DEP)3]n (1). Triethyl phosphate (3.31g, 3.1 mL, 18 mmol) was added to a solution of NdCl 3 (0.93 g, 3.6 mmol) in ethanol (40 mL) and DMSO (5mL) and the resulting pale violet solution was stirred at 40 °C for 30 minute. Then, it was left to evaporate slowly at room temperature. After two months, colorless prismatic crystals of 1 were isolated (yield 1.62 g, 74.56%, m.p < 300 o C). IR (KBr, ): 2984s, 2940m, 2912m (νCH), 1446w, 1399m, 1372w, 1197s, 1181s, 1168s, 1117s, 1093s, 1066s, 1044s (νC-O-P), 977s, 825s, 778m (νP-O), 576m, 541m, 504m, 409w, 388m, 332w (νNd-O

Neodymium(III) Complexes of Dialkylphosphoric and Dialkylphosphonic Acids Relevant to Liquid–Liquid Extraction Systems

“…Compound 1 is isostructural with Sm­(DMP) 3 and Eu­(DMP) 3 . The structure is also similar to that of La­(DMP) 3 and Nd­(DEP) 3 (where DEP – is the deprotonated form of diethylphosphoric acid) . In the latter cases, the local environment around the lanthanide ion also consists of six (RO) 2 POO – groups bridging to adjacent lanthanide ions to form polymeric networks.…”