N. P. Nesterova

CORRELATION ANALYSIS OF ARYLIC STRENGTHENING OF THE EXTRACTION CAPACITY OF BIDENTATE ORGANOPHOSPHORUS EXTRACTANTS

This paper is devoted to the so-called effect of “anomalous arylic strengthening” (AAS) observed upon extraction of a series of elements, mainly actinides and lanthanides, by bidentate neutral organophosphorus compounds (BNOPC). This “anomalous” effect is an increase in the extraction capacity of a reagent when alkyl substituents at the phosphorus atom are replaced with more electronegative aryl groups. The influence of phenyl substituents at the phosphorus atom on the reactivity of organophosphorus compounds of various types was considered. Based on the data on electronic effects of substituents, hypotheses were formulated about the reasons for AAS involving phenyl groups that are biphilic because they have substituents capable of manifesting both donor and acceptor properties depending on several factors such as,e.g., the nature of the reaction center, the character of the attacking reagent, the nature of the solvent,etc. When a strong complex of a metal with a phenyl substituted reagent of BNOPC is formed during extraction, the phenyl groups become donating, and additional strengthening of the complex appears.

Oxides of dialkyl(diaryl)[dialkylcarbamoylmethyl]phosphines

Conclusions1.Oxides of dialkyl(diaryl)[dialkylcarbamoylmethyl]phosphines have been synthesized and characterized.2.The character of the substituents on the phosphorus atom substantially influences the extraction properties of the compounds obtained with respect to Am(III), the p-phenyl-substituted derivatives being most effective.

Reaction of carbamoylmethylphosphoryl compounds with nitric acid

Conclusions1.Using thermometric titration and IR spectroscopy, we investigated the reaction of carbamoylmethylphosphoryl compounds (CMP) and of some monophosphoryl compounds with HNO3 in dichloroethane and in CCl4.2.The interaction between CMP and HNO3 takes place in two stages with sharply different ΔH values which correspond to the formation of molecular complexes at the P=O and C=O groups.

Dialkyl(Aryl) [Dialkylcarbamoylmethyl]Phosphine Oxides as Extractants for Concentrating of Transplutonium Elements from Acid Media

Abstract Dialkyl(aryl)carbamoylmethylphosphine oxides (CMPO), prepared by interaction of tervalent phosphorus acid esters with chloracetic amides R1R2P(O)CHR4C(O)NR3 2, R1, R2, R3, R4 = Alkyl or Aryl, can be used successfully for concentrating the transpluto-nium elements.

Carbamoylmethylphosphoryl Compounds: Ch-Acidity and Basicity

Abstract Carbamoylmethylphosphoryl compounds (CMP) are used as neutral bifunctional extractants. However, little is known about acid-base properties of these compounds. We have studied CH-acidity and basicity of selected CMP, RR′P(O)CH2C(O)NEt2 with R,R′ = Alk, Alk2N, Ar, AlkO, and also H-complexes of CMP with HNO3.

Investigation of EPR spectra of anion radicals of alkylenediphosphine dioxides and diaryl (carbamoylmethyl)phosphine oxides

It has been found that the length of the alkylene bridge in anion radicals of alkylenediphosphine dioxides influences the EPR spectra — an effect that is related to differences in structure of the ion pair. Temperature-dependent changes in the EPR spectra of anion radicals of diaryl (carbamoylmethyl)phosphine oxides are related to retarded rotation of the fragments of the anion radicals around the C-C bridge bond.

Coordination compounds of alkali metals and copper with cambamoyl phosphine oxide derivatives

Conclusions1.Stability constants for alkali metal complexes of composition [ML]+ and a copper complex [CuLCl]+, which are formed via treatment of alkali metal 2,4-dinitrophenolate or copper chloride with a series of carbamoyl phosphine oxide derivatives, have been determined in anhydrous solutions.2.The most stable complexes are formed by ligands containing an aryl substituent attached to the phosphorus atom.

Tertiary Carbamoylmethylphosphine Oxides and their Analogs

Abstract Dialkyl(diaryl)Carbamoylmethylphosphine oxides (I) were prepared by interaction of tervalent phosphorous acid esters with chloracetic amides:

Complexes of alkylenediphosphine dioxides with uranyl nitrate

A number of complexes of tetraaryl (alkyl) alkylenediphosphine dioxides with uranyl nitrate have been synthesized. Coordination of both P=O groups with the uranyl ion is observed in the complexes of methylenediphosphine and cis-tetraarylvinylenediphosphine dioxides; in complexes of trans-tetraaryl (alkyl) vinylenediphosphines, only one P=O group is involved in complexing. Tetraphenylethylenediphosphine dioxide forms both types of complexes.

Acid-base properties of phosphorus compounds 13. Reaction of diphosphoryl compound with nitric acid

1. The dioxides of the alkylenediphosphines and the tetraethyl esters of the alkylenediphosphonic acids have been titrated with nitric acid in chloroform and dichloroethane solutions. In reacting with compounds of this type, the HNO3 attacks both phosphoryl groups to form a 2∶1 H-complex. The heats of formation of such complexes in CHC13 have been determined. 2. The complexes of the various compounds with HNO3 have been separated out in crystalline form and their IR spectra studied.