The general approach to a novel class of functionalized ionic liquids 4–6 bearing grafted diphenylcarbamoylmethylphosphine oxide complexing groups in the cation has been elaborated. The synthetic route comprises the preparation of the intermediate (diphenylphosphorylmethylcarbamoyl)propylimidazole 3, followed by sequential quaternization by alkyl halides (chlorides or bromides) and anionic exchange in the case of ionic liquids bearing the hexafluorophosphate anion. The structures of two ionic liquids were confirmed by X-ray analysis, revealing the strong intramolecular hydrogen bond formed by the acidic protons of the heterocycle and oxygen atom either of the PO or CO group, depending on the anion nature. In neutral media, these ionic ligands form complexes ML₂ with europium chloride or europium nitrate via an O,O-bidentate mode similar to known neutral CMPO compounds. The solid phase extractants prepared by immobilization of these FILs on solid matrixes possess sorption activity towards actinides and rare-earth elements in nitric acid solutions.

Novel unsymmetrical SCS′-pincer ligands, 1-[PhNHC(S)]-3-[Ph₂P(S)NH]-C₆H₄ (3) and 1-[PhNHC(S)]-3-[Ph₂P(S)O]C₆H₄ (7), bearing a thiocarbamoyl moiety in combination with thiophosphorylamino- and thiophosphoryloxy-donating groups, respectively, were obtained via thiophosphorylation of 3-amino- and 3-hydroxy-benzoic acid (thio)anilides 1 and 6. Direct cyclometallation of the central benzene ring in the ligands 3 and 7 in reaction with (PhCN)₂MCl₂ (M = Pd, Pt) as a metal precursor afforded κ³-SCS′-hybrid pincer complexes 8, 9 with 5- and 6-membered fused metallacycles in good to high yields (67–95%). The complexes 8 and 9 were characterized by multinuclear NMR (³¹P, ¹H, ¹³C) and IR spectroscopy as well as single-crystal X-ray crystallography. Palladium complexes 8a and 9a were shown to be active catalysts for the Suzuki–Miyaura cross-coupling reaction. In the solid state the ligands 3 and 7 as well as their Pt(II) and Pd(II) complexes 8 and 9 are luminescent at 300 K. The emission of the complexes has the different origin depending on the metal nature.

Novel unsymmetrical ligands, 1-thiophosphoryloxy-3-thiophosphorylbenzenes 3a–d, bearing phosphine sulfide and thiophosphoryloxy moieties as coordinating sites, were found to undergo cyclometalation at the C-2 position of the central benzene ring in a reaction with bis(benzonitrile)palladium dichloride affording rare examples of nonsymmetrical pincer complexes, namely [2-{(thiophosphoryl)oxy}-6-(diphenylthiophosphoryl)phenyl]palladium chlorides 4a–d, containing 5- and 6-membered fused metallacycles with κ³-SCS′-coordination. Molecular structures of the complexes were characterized by X-ray diffraction. These complexes demonstrated high catalytic activity for the Suzuki cross-coupling reactions of aryl bromides with phenylboronic acid.