D. I. Lobanov

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.

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.

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 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.

Correlation of nucleae quadrupole resonance frequencies with some chemical constants in the aliphatic series

Linear relationships are established between the nuclear quadrupole resonance frequencies of alkyl chlorides, RCl, on the one hand, and the pKa values of RCOOH and RNH2 as well as the Taft σ* constants, on the other hand. Similar linear correlations were found between the NQR frequencies of the substituted compounds XCH2Cl and the pKa of XCH2COOH, XCH2NH2, XCH2OH, as well as the σ* constants of XCH2 radicals, where X are electronegative substituents. X substituents with unshared electron pairs (RO, RS, F, Cl, Br) are an exception; nevertheless, the deviation of these points is regular and depends linearly on the resonance parameters σR0or σR of the X substituents. The relationships can be used for an approximation of the ionization constants of a number of fatty acids, for the calculation of the Taft σ* constants of radicals R and XCH2 and of the resonance parameters σR0and σR of X substituents with an accuracy which in many cases is in no way inferior to that of the experimental values, and also for the approximate evaluation of the ionization constants of XCH2NH2 amines and XCH2OH alcohols.

P,O-Ligands. Complexes of tetraphenylmethylenediphosphine oxide with silver nitrate

The 1 : 1 and 1 : 2 complexes of AgNO3 with Ph2PCH2P(O)Ph2 were prepared and their structures were established by IR and 31P NMR spectroscopy and X-ray diffraction analysis. The crystal of the 1 : 1 complex consists of centrosymmetric dimers based on the ten-membered macrocycle AgOPCH2PAgOPCH2P. Each neutral ligand serves as a bridge between two silver ions, the latter being coordinated by the NO3 group in the monodentate fashion. In the 1 : 2 complex, the dimeric structure is retained, but both NO3 groups are replaced by the ligand molecules.

1,1- Bis(diphenylphosphinoyl)ethanol. Synthesis and complexes with neodymium and copper nitrates

A preparative method for the synthesis of 1,1-bis(diphenylphosphinoyl)ethanol (1) has been elaborated. In CHCl3 and MeCN solutions compound1 is associated into H-bonded dimers (-ΔH ≈ 12 kcal mol−1). Complexes of compound1 with NdIII, CuII, and CuI nitrates have been studed. The H-bonded dimers are retained upon complexing.

Synthesis of Hexa- and Pentacoordinated Phosphorus Compounds from White Phosphorus

Abstract A new method is developed for the synthesis of phosphoranes (IIIa-d) and phosphorates (IVa-d) starting from substituted o-benzoquinones(Ia-d), catechols(IIa-d) and white phosphorus.

The Structure of o-Hydroxyaryloxy-bis-(o-arylenedioxy)-phosphoranes and their Acid-Base Properties

1. We have obtained crystalline phosphoranes with o-hydroxyphenyl substituent and we have studied their vibrational, electronic, and NMR spectra, and also the spectra of the products of their reaction with nitrogen bases. 2. The molecular structure with a five-coordinate phosphorus atom corresponds to the investigated phosphoranes; and the ionic structure with a six-coordinate phosphorus atom corresponds to the phosphorates. 3. A new type of acid-base interaction has been established, connected with the fact that the process of proton transfer is accomplished by phosphorane-phosphorate conversions; in this case the hydroxyl group in the phosphorane molecule displays enhanced acidity, and yields products of complete proton transfer with different bases.

Nucleophilicity constants of some groups containing pentavalent phosphorus

1. The ionization constants of certain meta- and para-substituted phenols were determined, and the constantsσ− andσm for the (CH3)2P(O)-, (CH3)2P(S)-, and (CH3)3P+- groups calculated from them. 2. The ability of the groups to undergo conjugative interaction in the data for the series shown above is somewhat less than that of the carbonyl-containing substituents (C2H5OOC- and CH3CO-).