Evidences for Chelating Complexes of Lithium with Phenylphosphinic and Phenylphosphonic Acids: A Spectroscopic and DFT Study

Abstract Lithium complexes were prepared with phenylphosphinic and phenylphosphonic acids. The complexes were studied in the solid state using Fourier transform infrared spectroscopy spectroscopy and in solution (methanol) using 1H, 13C, and 31P Nuclear magnetic resonance spectroscopy (NMR) spectroscopy; the most preferred structures of the complexes were determined by density functional theory (DFT) computational method. Although methanol has a strong solvation effect on lithium ions and ligands, which causes dissociation of the complexes, significant changes of the NMR spectra of the complexes (relative to those of the free ligands) were observed. The new spectroscopic results indicate the presence of the phenylphosphinic acid tautomer (I: C6H5PH(˭O)OH) rather than that of phenyl-phosphorous acid (II: C6H5P(OH)2) in deuterated methanol showing PH/PD exchange. On the other hand, tautomer I predominates in the complex with lithium without showing PH/PD exchange. The DFT calculations predict that tautomer ...