Olga V. Bykhovskaya

Complexation of [ω-diphenylphosphinoalkyl]diphenylphosphine sulphides with AgNO3

By reaction of [ ω -diphenylphosphinoalkyl]diphenylphosphine sulphides Ph 2 P(CH 2 ) n P(S)Ph 2 ( n = 2–4) (L 1 −L 3 ) with AgNO 3 in CH 3 CN crystalline complexes with the composition metal:ligand 1:1 [Ag(L 1 )NO 3 , Ag(L 2 )NO 3 , Ag(L 3 )NO 3 ] and 1:2 [Ag(L 1 ) 2 NO 3 , Ag(L 3 ) 2 NO 3 ] were isolated. According to the X-ray analysis data, the crystals of Ag(L 1 )NO 3 are constructed from centrosymmetric dimeric molecules based on the 12-membered macrocycle AgSPCH 2 CH 2 PAgSPCH 2 CH 2 P ¯ . Each of the neutral ligands L 1 is a bridge between two silver ions and each of the silver ions is coordinated by a chelating NO 3 group. According to the IR spectra, the other 1:1 complexes also have an analogous structure. In the 1:2 complexes the coordinated NO 3 groups of the 1:1 complexes are replaced by the phosphine sulphide ligand. The downfield shifts of the signals of P III and P V atoms in 31 P NMR spectra of 1:2 complexes in comparison with the free ligands L 1 and L 3 reflect a participation of the P III atom and P=S group in complex formation.

Complexation of (N, N-diethylthiocarbamoylmethyl) diphenylphosphine sulfide with silver nitrate. The structure of the [Ag{Ph2P(S)CH2C(S)NEt2}2]NO3 complex

Abstract(N, N-Diethylthiocarbamoylmethyl)diphenylphosphine sulfide, Ph2P(S)CH2C(S)NEt2, forms a distorted tetragonal bisligand complex [AgL2]NO3 with Ag+. The stability constant of the complex in acetonitrile was estimated by spectrophotometry (logK=3.7).

Intramolecular P=S and P=N Alkylation. General Method for Synthesizing 1,2-Heteraphosphacyclanes

Results have been generalized for investigations on the synthesis of 1,2-thiaphosphacyclanes by intramolecular P=S alkylation of ω-haloalkyl substituted compounds of four-coordinated phosphorus with a P=S bond. The method has been extended to nitrogen-containing analogs with a P=N bond. A new general method is proposed for the synthesis of 1,2-thia- and 1,2-azaphosphacyclanes.

RING-CHAIN HALOGENOTROPIC TAUTOMERISM. 2,2-DIPHENYL-1,2ι4-THIAPHOSPHOLANIUM BROMIDE ⇋ 3-BROMOPROPYLDIPHENYLPHOSPHINE SULFIDE

Abstract A new type of ring-chain anionotropic tautomerism for cyclic thiaphospholanium bromide 2A and isomeric phosphine sulfide 2B was investigated. Both of the tautomers were isolated in crystalline form. Their structures were proved by IR, Raman, 1H, 31P NMR spectroscopy and X-ray analysis. In solution the equilibrium position doesnt depend on the kind of dissolved tautomer. The effect of the solvent. concentration and temperature on the equilibrium 2A ⇋ 2B was studied as well as kinetics of interconversion of tautomers.

Synthesis of 1,2-azaphospholanes containing an amino acid fragment

Abstract2-Oxo-1,2-azaphospholanes and 1,2-azaphospholanium salts containing an amino acid fragment were synthesized by intramolecular P-alkylation of N-3-chloropropyl-substituted tricoordinate phosphorus amides. Hydrolysis of 2-oxo-1,2-azaphospholanes at the P-N bond gives rise to γ-aminopropylphosphonic acid derivatives.

Synthesis of 1,2-Azaphosphacyclanes; Generality of the Mechanism of P=N Alkylation and Arbuzov Reaction

A novel convenient one-pot synthesis of 2-oxo-1,2 u 5 -azaphosphacyclanes 1 and 1,2 u 4 -azaphosphacyclanium salts 2 via intramolecular N-alkylation of y -halogenalkyl-substituted iminophosphoryl compounds 3 has been developed. The common nature of the reaction of intramolecular cyclization of iminophosphoryl compounds having an alkoxy group at the phosphorus atom and the Arbuzov reaction has been established.

P,S-Ligands. Complexes ofP,P,P′,P′-tetraphenylethylenediphosphine monosulfide with PdCl2

Abstract1:1 and 1:2 complexes of Ph2P(CH2)2P(S)Ph2 with PdCl2 were synthesized. Their structures were established by31P NMR and IR spectroscopy and X-ray diffraction analysis. In the crystals, the 1:1 complex has a chelate structure. In CH2Cl2, this complex partially dissociates at the Pdxad.S=P bond. According to the X-ray diffraction data, only the PIII atoms the cationic chelate complex [Pd(Ph2P(CH2)2P(S)Ph2)2]2+ 2NO3−.

SYNTHESIS AND SOME TRANSFORMATIONS OF 1, 2-HETEROPHOSPHACYCLANES

The general pathway to 1,2-monoheterophosphacyclanes via intramolecular S-and N-alkylation of ω-halogenoalkylsubstituted thiophosphoryl and iminophosphoryl compounds has been developed. Intramolecular alkylation of 3-and 4-halogenoalkyldiphenylphosphine sulfides results in 1,2λ4-thiaphospholanium and thiaphosphorinanium halogenides. In solution of these compounds the rare ring-chain halogenotropic tautomerism has been observed and investigated in detail. Intramolecular Pishchimuka rearrangement of the esters of ω-halogenoalkylsubstituted thiophosphorus acids was found to be a synthetic route to 2-oxo-1,2λ5-thiaphospholanes and thiaphosphorinanes.

Complexes of (ω-diphenylphosphinoalkyl)diphenylphosphine sulfides with silver nitrate in pyridine

The behavior of the phosphine-phosphine sulfide complexes of silver, [Ph2P(S)(CH2)nPPh2]m·AgNO3 (n=2 or 4;m=1 or 2), in pyridine was studied. Dissolution of the 1:1 complexes in pyridine leads to destruction of their dimeric structures Ag2[Ph2P(S)(CH2)nPPh2]2(NO3)2 (A) to form the complexes Agpy+−P(Ph2)(CH2)nPh2P=S and Agpy+−S=PPh2(CH2)nPPh2. The solid complexes isolated from pyridine restore dimeric structure A. According to the data of X-ray diffraction analysis, the 1:2 complex isolated from pyridine has the structure [S=P(Ph2)(CH2)2(Ph2)P−(NO3)Ag(Py)−P(Ph2) (CH2)2(Ph2)P=S]Py. According to the data of IR spectroscopy, dissolution of this complex in chloroform leads to the formation of the dimeric structure Ag2Ph2P(S)(CH2)2PPh2]4(NO3)2.

N-Phosphoryl-2-oxo-1,2-azaphospholanes: First Example of Cyclic O,O-Bidentate Ligands with the P-N-P Backbone

Abstract A convenient one-pot synthesis of N-phosphoryl-2-oxo-1,2-azaphospholanes was developed starting from commercially available or simple-to-prepare phosphorus (III) acid chlorides and 3-bromopropylamine. The compounds readily form complexes with f-elements of ML, ML2, and M2L3 composition including (μ2-peroxo)-bridged uranium complexes, depending on both the ligand and metal nature.