Tetraalkyl Hydroxymethylene-bisphosphonate and Dialkyl 1-Diphenylphosphinoyl-1-hydroxy-ethylphosphonate Derivatives by the Pudovik Reaction and Their Rearranged Products

The reaction of diethyl α-oxoethylphosphonate and diethyl oxobenzylphosphonate with diethyl phosphite, dimethyl phosphite, and diphenylphosphine oxide affords, depending on the substrates and conditions (nature and quantity of the amine catalyst, temperature, and solvent), the Pudovik adduct and/or the corresponding >P(O)–CH–O–P(O)< product formed by rearrangement. The nature of the substituent on the central carbon atom (a methyl or phenyl group) influences the inclination for the rearrangement. The asymmetric products (either adducts or rearranged species) with different P(O)Y functions (Y = RO or Ph) exhibit interesting NMR features.

An approach towards the synthesis of lithium and beryllium diphenylphosphinites

The diphenylphosphinites [(THF)Li(OPPh2)]4 and [(THF)2Be(OPPh2)2] have been synthesized via direct deprotonation of diphenylphosphine oxide with n BuLi and BePh2, respectively, as well as via salt metathesis. These compounds were characterized by multinuclear NMR spectroscopy, and the side-products of the reactions obtained under various reaction conditions have been identified. The beryllium derivative could not be isolated and decomposed into diphosphine oxide Ph2PP(O)Ph2. The solid-state structure of this final product together with that of [(THF)Li(OPPh2)]4 have been determined by single-crystal X-ray diffraction.

Direct Copper-Catalyzed C-3 Arylation of Diphenylphosphine Oxide Indoles

We have developed a simple and effective method for the preparation of C-3 arylation of phosphorus-containing indole compounds in the presence of CuI under mild conditions. This reaction provided a reliable method for the modification of the ligands.

Syntheses and Study of a Pyrroline Nitroxide Condensed Phospholene Oxide and a Pyrroline Nitroxide Attached Diphenylphosphine

The reaction of a diene nitroxide precursor with dichlorophenylphosphine in a McCormac procedure afforded 1,1,3,3-tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole-5-oxide-2-oxyl. Lithiation of the protected 3-iodo-pyrroline nitroxide followed by treatment with chlorodiphenylphosphine after deprotection afforded (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-3-yl)diphenylphosphine oxide, and after reduction, (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-3-yl)diphenylphosphine was realized, which was also supported by X-ray single crystal diffraction measurements. This pyrroline diphenylphosphine derivative was converted to hexadecylphosphonium salt, which is an analogue of antineoplastic agent, MITO-CP.

Solvent-Impregnated Resins Based on the Mixture of (2-Diphenylphosphoryl)-4-ethylphenoxy)methyl) diphenylphosphine Oxide and Ionic Liquid for Nd(III) Recovery from Nitric Acid Media

Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene–divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C4mim]+[Tf2N]−for the extraction chromatography recovery of Nd(III) from nitric acid solutions. It was shown that introduction of the ionic liquid into the SIR composition results in considerable enhancement of the Nd(III) recovery efficiency compared with resin impregnated only by L in slightly acidic media. The influence of the L: ionic liquid molar ratio in the SIRs composition, their percentages, concentration of metal and HNO3 in the eluent, and acid type on the value of synergistic effect and adsorption efficiency of Nd(III) recovery was studied. The SIR containing 40% of mixture of L and [C4mim]+[Tf2N]− with molar ratio 2:1 turned out to be the most efficient. The selectivity of Nd(III) separation from light and heavy rare-earth elements was studied and the optimal conditions of Nd(III) adsorption recovery and stripping by this SIR were chosen. It was found that in recovery efficiency of Nd(III) developed SIR exceeded the SIR containing Cyanex 923 (a mixture of monodentate trialkylphosphine oxides) and [C4mim]+[Tf2N]−.

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies

With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5–7, where the ArP(O)Ph2 group of phosphine oxide type is replaced by phosphonic fragments. Quantum-chemical modelling of the structures of phosphoryl-containing podands 1 and 5–7 has been performed, which was later confirmed by the data of X-ray diffraction. The features of extraction of nitric acid, as well as U(VI), Th(IV), Nd(III), and Ho(III) with compounds 1 and 5–7 from nitric acid media into 1,2-dichloroethane have been studied. The compositions of extracted complexes have been determined.

Metal-free visible-light-induced photoredox-catalyzed intermolecular pyridylation/phosphinoylation of alkenes

A visible-light-induced and photoredox-catalyzed intermolecular pyridylation/phosphinoylation of alkenes using 4-cyanopyridine and diphenylphosphine oxide under mild metal-free conditions has been reported.

Efficiently luminescent heteroleptic neutral platinum(II) complexes based on N^O and N^P benzimidazole ligands

A series of new luminescent cycloplatinated(II) complexes (5a-8a and 5b-8b) with formula Pt(bt)(N^O) and Pt(bt)(N^P) have been synthesized [bt = phenylbenzothiazole, N^O =(2-(1H-benzimidazole)-phenyl)diphenylphosphine oxide derivatives for 1a-4a and N^P =...