V. A. Miluykov

The influence of different substituents on the geometrical changes in the heterocyclic moiety of 1,2-diphospholes

GRAPHICAL ABSTRACT ABSTRACT It is shown that increase of steric bulk of R group of 1R-1,2-diphospholes results in decrease of the pyramidality of P(III) atom, but has little impact on a planarity of the entire heterocycle in the case of R = Alk. At the same time, planarization of the heterocycle reported elsewhere for R = SnMe3 or SiMe3 is accompanied by moderate increase of the P(III) pyramidality relative to the case of R = Alk. This difference could be related to effects of π-σ conjugation between P-Sn/P-Si moiety and the dienic system of the 1,2-diphosphole.

Conjugation effects and optical spectra of 1,2-diphosphole cycloadducts

Quantum chemical calculations and a comparative analysis of Raman spectra of 3,4,5-triphenyl-1-propyl-1,2-diphosphole (1), anti-endo-4,7,8,9-tetraphenyl-10-propyl-4-aza-1,10-diphosphatricyclo[5.2.1.02,6]deca-8-ene-3,5-dione (2) and 1,2,6,7-tetraphospha-3,4,5,8,9,10-hexaphenyltricyclo[5.3.0.02,6]deca-3,9-diene (3) made it possible to explain considerable differences in the UV absorption spectra of these compounds. The phenyl groups in the compounds under study, despite the steric factor, are conjugated with the π-system of the heterocycle, which in the case of diphosphole 1 comprises π-electrons of the C=C and P=C bonds. The disturbance of this diene system in molecules 2 and 3 decreases the effective length of conjugation of phenyl groups with the attached double bonds of the phosphorus-containing ring, that results in the hypsochromic shift of the π—π* electron transition bands in the UV absorption spectrum from 411 to 312 nm. The formation in molecule 3 of the four-membered ring P4, which is a new chromophore group, leads to the appearance of an additional absorption band with the maximum at ∼342 nm.

Synthesis, characterization, and application of phosphonium ionic liquids

GRAPHICAL ABSTRACT ABSTRACT Phosphonium salts containing sterically demand head group are particular subclass of ionic liquids that have potentially broad application in both academia and industry. The synthesis, physical chemical properties, and application in stabilization of palladium nanoparticles and in electrochemistry are briefly reviewed.

Novel phosphonium salt for paste electrode to study the redox properties of insoluble compounds

GRAPHICAL ABSTRACT ABSTRACT A new carbon paste electrode is described, which contains the room temperature ionic liquid tri(tert-butyl)(decyl)phosphonium tetrafluoroborate as a binder. The advantages of this electrode are a high conductivity, very wide electrochemical window (5.4 V from 2.7 V to −2.7 V, one of the widest ever reported for RTILs), stability in time, and reproducibility.

Synthesis and structure of the iron(iii) tris-chelate complex based on 1,1´-ferrocenediylbis(phenylphosphinic acid)

The previously unknown isomorphous tris{µ2-[1,1´-ferrocenediylbis(phenylphosphinato)]}-iron(iii) complexes as solvates with methanol and DMSO were synthesized and characterized.

Structure and supramolecular organization of tri-n-butyl(octadecyl)phosphonium tetrafluoroborate and its influence on catalytic activity of stabilized palladium nanoparticles

A crystal structure and aggregation properties of tri-n-butyl(octadecyl)phosphonium tetrafluoroborate were studied. Palladium nanoparticles stabilized by this phosphonium salt exhibit different catalytic activity in the Suzuki reaction, depending on the concentration of the stabilizing agent, which is related to the supramolecular organization of the Pd–phosphonium salt system.

The Chemical Properties of Alkali Metals Heptaphosphides

Trisodium heptaphosphide Na3P7 (1) reacts with alkyl tosylates with formation of sodium dialkylheptaphosphides (2) or trialkylheptaphosphines (3) depending on the stoichiometry. Sodium 1,2-diphosphacyclopentadienide is formed in the reaction of cyclopropenyl complexes of nickel with sodium polyphosphides.

Ferrocene-Containing Sterically Hindered Phosphonium Salts

The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations between their structures and electrochemical properties. The elongation of the alkyl chain at the P atom as well as replacement of the Br− anion by [BF4]− shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br− anion destabilizes the corresponding ion pair, making its oxidation easier due to increased highest occupied molecular orbital (HOMO) energy. Increased HOMO energy for ion pairs with the Br− ion compared to BF4− are caused by contribution of bromide atomic orbitals to the HOMO. The observed correlations can be used for fine-tuning the properties of the salts making them attractive for applications in multicomponent batteries and capacitors.

Electrochemical properties of poly(manganese 1,1′-ferrocenediyl-bis(H-phosphinate))

GRAPHICAL ABSTRACT ABSTRACT A new carbon paste electrode with the decyl(tri-tert-butyl)phosphonium tetrafluoroborate binder was prepared and successfully used for the study of the redox properties of the insoluble coordination polymers involving manganese and iron metallocenters.

Specific features of the chemical behavior of sodium 3,4,5-tris(2-thienyl)-1,2-diphosphacyclopentadienide

A new representative of 1,2-diphosphacyclopentadienide anions containing 2-thienyl substituents at carbon atoms was synthesized by the reaction of sodium polyphosphides with cyclopropenylphosphonium salts. The specific features of the chemical behavior of this compound were revealed by studying the reactions with organic and heteroorganic electrophiles and with pentacarbonylmanganese bromide.