Anilidophosphine ligand supported praseodymium and terbium phosphaethynolate complexes: Synthesis, characterization, and DFT calculations

The 2-phosphaethynolate has received particular attention and displayed various reaction patterns due to its ambident property. In this work, the reactivity of monoanionic bidentate anilidophosphine PN ligand (PN: <i>N</i>-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethyl anilide) supported (PN^Me3)₂Pr^IIICl (<b>2A</b>) and (PN^Me3)₂Tb^IIICl (<b>2B</b>) with NaOCP(dioxane)_2.5 by salt elimination reaction is described. The reactions yield corresponding praseodymium and terbium phosphaethynolate complexes: (PN^Me3)₂Pr^IIIOCP (<b>3A</b>) and (PN^Me3)₂Tb^IIIOCP (<b>3B</b>), respectively. These two complexes feature a preferential O-bound terminal adduct. Magnetic data analysis reveals that praseodymium and terbium chloride and phosphaethynolate complexes showed a strong temperature dependence. All the complexes have been characterized by various measurement means, including NMR, UV spectroscopies, FT-IR spectrum as well as X-ray single crystal crystallography. For comparison, bond analyses of all the complexes collected from experimental and computational approaches are conducted in detail.