V. V. Zverev

Proton-acceptor properties of azahomofullerene and fullerenoaziridine containing a cyanuric acid fragment

Abstract13C and 1H NMR and UV spectral studies on 1,3-diallyl-5-[4-(azahomo[60]fullereno)butyl]hexahydro-1,3,5-triazine-2,4,6-trione ([5,6]-open isomer) and 1,3-diallyl-5-[4-(aziridino[60]fullereno)butyl]hexahydro-1,3,5-triazine-2,4,6-trione ([6,6]-closed isomer), as well as quantum-chemical calculations, showed that only the latter possesses weakly basic properties.

Electronic and Steric Structure of the Methanofullerene C61(CO2Me)[P(O)(OMe)2]. A Density Functional Study

The asymmetric addend in the methanofullerene C61(CO2Me)[P(O)(OMe)2] polarizes and divides the fullerene shell into four nonequivalent fragments. According to DFT/PBE calculations, the most stable conformers of the methanofullerene C61(CO2Me)[P(O)(OMe)2] involve Coulomb interactions of the phosphoryl oxygen with one of the fullerene carbon atoms, which produces polarization of the corresponding fragment and asymmetry in bond lengths and atomic charges in the fullerene shell. Alternation and attenuation of changes in bond lengths along the conjugation branches was revealed.

Synthesis and structure of 1,3,4-oxaza(thiaza)phospholines

Bis(chloromethyl)phosphinic (-phosphinothioic) iso(thio)cyanates add secondary amines to form N-phosphorylated (thio)ureas, which cyclize in the presence of a base to 1,3,4λ5-oxaza(thiaza)phospholines. Phosphorylated ureas obtained by addition of ammonia and primary amines to chloromethylphosphonic (-phosphinic) isocyanates cyclize to give 1,4,2-diazaphospholidines or 1,3,4-oxazaphospholines. Prototropic transformations in the series of 1,3,4λ5-oxazaphospholines were revealed; the electronic and steric structures of the tautomers were studied. Chloromethylphosphonothioic (-phosphinothioic) isothiocyanates add primary amines to give 1,3,4λ5-thiazaphospholines.

Theoretical investigation of interaction of hydrogen dithiophosphate with 2-phenyl-2H-1,2,3-diazaphosphole

We showed previously that the cyclic two-coordinate phosphorus derivative—5-methyl-2-acetyl(phenyl)-2H-1,2,3-diazaphosphole— takes up O,O′-dialkyl hydrogen phosphorothioand dithioates across the σ 2λ3P C bond; the anionic moiety of the thio and dithio acid was directed toward the two-coordinate phosphorus atom.1 In the 31P NMR spectra of the resulting 3-(dialkoxyphosphinoyldithio)-2-phenyl1,2,3-diazaphospholines 1 the chemical shifts of the three and four— coordinate phosphorus atoms were equivalent owing to intramolecular interaction of the P(III) atom with the thione sulfur atom in the adduct. As a continuation of these studies, the electron and molecular structure of adduct of hydrogen dimethyl dithiophosphate with 2phenyl-5methyl-2H-1,2,3-diazaphosphole, containing P C bond, have been studied by the methods of quantum chemical calculations (MNDO, PM3, ab initio) with the usage of the photoelectron spectrosopy. It has been shown, that the equality of the shifts of P(III) and P (IV) in 31P NMR spectra of the adduct 1 probably takes place in the results of the real of the structure with nearly equal lengths of four P S bonds.

Quantumchemical Investigation of Unsaturated Sixmembered Heterocycles: I. Steric and Electronic Structures of 1,2-dihydro-1,2-azaphosphorin

By quantumchemical calculations of 1,2-dihydro-1,2-azaphosphorin by semiempirical and abinitio calculations we discovered that in gas phase it has twist form with planar nitrogen and pyramidal phosphorus atoms, the latter with a pseudoaxial substituent. The N-H and P-H bonds occupy anticlinal positions.

Synthesis and properties of O,O-dialkyl [1-hydroxy-3-(dialkylamino)-2,2-dimethylpropyl]phosphonates

O,O-Dialkyl [1-hydroxy-3-(dialkylamino)-2,2-dimethylpropyl]phosphonates were prepared for the first time. By means of NMR 1H, IR spectroscopy and quantum-chemical calculations the presence in them of various H-bonds was established. In the crystalline state P=O…HO intermolecular hydrogen bonds favor the formation of cyclic dimer associates DP=O. In the liquid state and concentrated solutions P=O…HO and N…HO intermolecular hydrogen bonds cause the formation of cyclic dimer associates DP=O and DN, and intramolecular hydrogen bonds provide the existence of different conformations of the monomer form MN, the most stable among them with the non-strained six-membered …NCCCOH… ring.

Electronic and steric structure of thermal isomerization products of 1-methyltricyclo[4.1.0.02,7]heptane radical cation

Distributions of the positive charge and unpaired electron in stable conformers of the thermal isomerization products of 1-methyltricyclo[4.1.0.02,7]heptane radical cation, having bicyclo[3.1.1]heptane, bicyclo[4.1.0]heptane, bicyclo[3.2.0]hept-6-ene, and 1,3-cycloheptadiene skeletons, were estimated by the PM3 semiempirical method.

Quantum-Chemical Investigation of Electronic and Spatial Structure of 1,2-Dihydro 1,2-Azaphosphorines and their Analogs

Abstract As part of our studies of 1,2-dihydrol-2-azaphosphorines (1.21. we have carried out obinifio investigation of the set of model six membred (hetero)cycles 1 and defined the influence of the bridge A-Z on the their parameters (3–21G* and 6–31G*, GAMESS, full optimization of geometry). In all structures studied only one twist conformer is realized. In PN structuns substitutients at the hetero atoms arc at different sides of the cycle, a substitutient at phosphorus beiig axial. The P atom is pyramidal, N atom is planar.