V. A. Milyukov

Application of time-dependent density functional theory and optical spectroscopy toward the rational design of novel 3,4,5-triaryl-1-R-1,2-diphospholes.

Twenty 3,4,5-triaryl-1-R-1,2-diphospholes were studied within the framework of density functional theory (DFT) and experimentally by UV/vis spectroscopy to check their suitability for opto-electronic applications. Time-dependent DFT (TD-DFT) calculations employing the PBE0 hybrid density functional combined with moderately sized def-TZVP basis set were shown to excellently reproduce the experimental absorption spectra of various 1,2-diphospholes. Frontier molecular orbital analysis reveals that HOMO and LUMO are mainly localized on the diphosphole ring and, to some extent, on the aryl moieties. The HOMO-LUMO energy gap can be easily tuned by variation of substituents introduced in para-positions of the aryl moieties and, to a lesser extent, by modification of the R group at phosphorus atom. As a result, both position and intensity of the absorption bands with highest wavelength are strongly influenced by the above structural changes. The UV-spectra simulations reveal that the introduction of donor groups like para-OMe, para-NMe2, and para-N(H)Ph, which are in n-π conjugation with the aryl moieties, should result in absorption of visible light by the corresponding 1,2-diphospholes, thus making them promising candidates for new functional materials.

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.

Synthesis and chemical properties of sodium 3,4,5-tris(diethylamino)-1,2-diphosphacyclopentadienide

Abstract1,2,3-Tris(diethylamino)cyclopropenylium iodide (1) reacted with sodium polyphosphides to give sodium 3,4,5-tris(diethylamino)-1,2-diphosphacyclopentadienide (2) in high yields. Chemical behavior of compound 2 in the reactions with organic and organoelement electrophiles was studied and compared with that of sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide.

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.

Supramolecular architecture of diammonium ferrocene-1,1′-diyldiphosphinates

Diammonium ferrocene-1,1′-diyldi(H-phosphinate) (1) and diammonium ferrocene-1,1′-diylbis(phenylphosphinate) (2) were obtained for the first time and structurally characterized. Compound 1 shows a supramolecular 3D structure in the crystal; the structure is stabilized by hydrogen bonds between the layers of ammonium cations and the layers of ferrocene-1,1′-diyldiphosphinate anions. The more hydrophobic and sterically crowded ferrocene-1,1′-diylbis(phenylphosphinate) anion of compound 2 together with ammonium cations and solvate water molecules forms supramolecular 2D layers in the crystal.

Cycloaddition reactions of 1-Alkyl-3,4,5-triphenyl-1,2-iphosphacyclopenta-2,4-dienes in the coordination sphere of tungsten carbonyl

Abstract1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes react with tungsten hexacarbonyl under the conditions of “indirect” replacement of the carbonyl group to give 1: 1 complexes; [4+2] cycloaddition reactions of these complexes with maleic acid derivatives and substituted acetylenes afford tungsten carbonyl complexes containing 10-alkyl-1,10-diphosphatricyclo[5.2.1.02.6]deca-8-ene-3,5-diones and 1-alkyl-2,3-diphenylphosphirenes, respectively.

On the formation of unusual complex salts in the ternary system M(NO3)2 (M = Ni, Co)-4,4′-bipyridine-biphenylene-4,4′-bis(methylphosphinic acid)

It was shown for the first time that the products of the reaction of biphenylene-4,4′-bis(methylphosphinic acid), 4,4′-bipyridine, and M(NO3)2 (M = Ni, Co) under the solvothermal synthesis conditions are complex salts with the phosphinate anion instead of the expected coordination polymers. The coordination environment of the nickel ion contains, along with water molecules, only one nitrogen atom of the 4,4′-bipyridine molecule, whereas the environment of cobalt includes two nitrogen atoms of two 4,4′-bipyridine molecules.

Synthesis and structure of an unusual pentanuclear complex of copper(I) with 3,4,5-tri- para -chlorophenyl-1,2-diphosphacyclopentadienide ligand

Unusual pentanuclear copper cluster based on 1,2-diphosphacyclopentadienide ligand was first synthesized and characterized by X-ray diffraction analysis.

Crystal packing of ammonium salts of arylenebis(phenylphosphinic) acids

It was shown for the first time that the crystal packing mode of the ammonium salt of thiophene-2,5-diylbis(phenylphosphinic acid) substantially differs from that of the dimethyl-ammonium salt of 1,4-phenylenebis(phenylphosphinic acid). The former crystal packing is a three-layer supramolecular sandwich structure consisting of two anionic layers separated by a layer of ammonium cations, whereas the supramolecular organization of the latter salt is based on alternating layers of anions and cations linked by hydrogen bonds.

REACTIONS OF THIOESTERS OF PHOSPHORUS ACIDS WITH CATIONIC COMPLEXES OF MANGANESE

Abstract The thioesters of P(III) acids react with [Cp(CO)2Mn(NO)]+ by substituting one CO-group with formation of a stable cationic products with a Mn-P bond. Fourier transform infrared spectroscopy and a special program were used for the real-time monitoring of the mechanistic path of the reaction of S-ethyl-N,N-tetraethyldiamidothiophosphite with [Cp(CO)2Mn(NO)] BF4 +. The formation of a few intermediates is described.