V. V. Ermolaev

Phosphonium ionic liquids based on bulky phosphines: synthesis, structure and properties

A series of new ionic liquids based on sterically hindered decyl(tri-tert-butyl)phosphonium (DTBP) or decyl(tricyclohexyl)phosphonium (DCHP) cations were prepared using quaternisation of tri-tert-butyl- or tricyclohexylphosphine with decylbromide and subsequent bromide exchange with the weakly-coordinating anions BF(4)(-), PF(6)(-), SO(3)CF(3)(-), N(SO(2)CF(3))(2)(-). The salts obtained melt below 100 degrees C and possess a broad electrochemical window. Density functional theory combined with X-ray crystallography, IR and Raman spectroscopy has been used to analyze the molecular and supramolecular structures of the compounds obtained and their possible influence on their physical properties.

Palladium nanoparticles stabilized by sterically hindered phosphonium salts as Suzuki cross-coupling catalysts

Palladium nanoparticles with an average size of 2.5±0.5 nm formed from palladium acetate in the presence of tri-tert-butyl(decyl)phosphonium tetrafluoroborate without an additional reducing agent exhibit high activity as a catalyst for the Suzuki cross-coupling reaction involving bromo- and chloroarenes under mild conditions.

Influence of the medium self-organization on the catalytic activity of palladium nanoparticles stabilized by amphiphilic phosphonium salts in the Suzuki reaction

The influence of the aggregation properties of the medium on the catalytic activity of palladium nanoparticles stabilized by amphiphilic phosphonium salts was demonstrated for the Suzuki coupling of bromoarenes and phenylboronic acid.

Decyl(Tri-Tert-Butyl)Phosphonium Tetrafluoroborate/Palladium Acetate: An Effective Catalyst for Cross-Coupling Reaction of Arylbromides with Phenylacetylene in Copper-Free Conditions

Abstract The phosphonium salts with sterically hindered cation and noncoordinating anion can be used as phase-transfer reagent in the Sonogashira cross-coupling reaction allowing copper- and amine-free protocol. The reactions proceed under mild conditions with good yields. GRAPHICAL ABSTRACT

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.

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.

Functionalized Phosphonium Ionic Liquids: Synthesis and Application

GRAPHICAL ABSTRACT Abstract A series of phosphonium salts with sterically hindered cation But3P+(CH2COOEt)X− (X = Cl, BF4, N(SO2CF3)2) (1) was prepared for the first time. Palladium nanoparticles (PdNPs) stabilized by (1) showed moderate activity as catalyst in Suzuki cross-coupling reaction of bromoarenes and phenylboronic acid.

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.