A. S. Balueva

First representative of optically active P-L-menthyl-substituted (aminomethyl)phosphine and its borane and metal complexes.

The first representative of 1,5-diaza-3,7-diphosphacyclooctanes (1) with chiral L-menthyl substituents on the phosphorus atoms was obtained by condensation of L-menthylphosphine with formaldehyde and p-toluidine. This optically active cyclic bisphosphine readily forms a stable P,P-complex with borane (2) and P,P-chelate complexes with platinum(II) (3) and palladium(II) dichloride (4). The structure of the bisphosphine 1 in solution was elucidated by employing a variety of 1D/2D NMR correlation experiments, and the molecular structure of complex 3 was studied by X-ray crystallography.

Intramolecular Interaction in Heterocyclic Phosphines

Some specific features of space structure, reactivity, complex formation and unusual physical properties of organic and organophosphorus compounds are due to univalent intramolecular interactions. Several intramolecular interactions observed in heterocyclic phosphines will be discussed in this current paper.

Structure, conformation, and dynamics of P,N-containing cyclophanes in solution.

3D structures in solution of highly symmetrical N,P-containing macrocycles were established by a variety of 2D NMR correlation techniques. It was shown that a number of magnetically equivalent fragments in such symmetrical systems can be estimated by NMR diffusion measurement. The title compounds adopt a helical conformation of the macrocycles in solution. The extent of twisting and the size of the intramolecular cavity are determined by steric hindrance of the aromatic substituents on the exocyclic phosphorus atoms with phenylene and dimethylmethylene groups forming the macrocycle. In solution these macrocycles host aromatic guests inside the cavity.

Synthesis and properties of 1-diphenylboryl-2-diphenylphosphino1,2-diphenylethene

Consecutive interaction of lithium phenylacetylide with triphenylborane and diphenylchlorophosphine gave 1-diphenylboryl-2-diphenylphosphino-1,2-diphenylethene, which is less reactive than dialkylborylphosphinoethenes.

Interaction of E-2-dibutylboryl-1-phenyl-1-diphenylphosphinohex-1-ene with diphenylketene and benzoyl(phenyl)diazomethane

A new betaine, 5,6,6-tributyl-2-diphenylmethylene-3,3,4-triphenyl-1-oxa-3-phosphonia-6-boratacyclohex-4-ene, and1-(benzoyl(phenyl)methyleneamino]-4,5,5-tributyl-2,2,3-triphenyl-2-phospha-I-azonia-5-boratacyclopenta-1,3-diene were synthesized upon interaction of E-2-dibutylboryl-1-phenyl-1-diphenylphosphinohex-1-ene with diphenylketene and benzoyl(phenyl)diazomethane, respectively. The structure of the latter product was established by IR spectroscopy and X-ray structural analysis.

Reaction of 1-boryl-2-phosphinoethenes with carbon disulfide

Abstract1-Butyl-1-dibutylboryl-2-diethylphosphino-2-phenylethene reacts with chloral and oxygen in a manner similar to 1-butyl-1-dibutylboryl-2-dipheylphosphino-2-phenylethene but, unlike the former, can also react with carbon disulfide to form a cyclic complex through an intramolecular S → B coordination bond; charge density transfer from sulfur to boron consisted of about 0.3 e.

An Effective Methodology of P,N-Macrocycles Design

The Mannich-type condensation in the systems: phosphine-formaldehyde-amine is an effective method of P,N-macrocycles design if bifunctional reagents are used.

Interaction ofZ-1,2-borylphosphinoalkene with ketenimine

N-Phenyl-C,C-diphenylketenimine adds toZ-1-butyl-I-dibutylboryl-2-diphenylphosphino-2-phenylethene to give 2,2,3-tributyl-6-diphenylmethylideno-1,4,5,5-tetraphenyl-1-aza-5-phosphonia-2-borataeyclohex-3-ene, which rearranges into 4,6-dibutyl-2-diphenylphosphino-1,1,3,5-tetraplienyl-3-aza-4-boradeca-1,5-diene upon heating. Its crystal structure has been established by X-ray analysis.

Synthesis of New Phosphines and P-Heterocycles from Phosphonates Containing Allyl Group

Addition of phenylphosphine to allylphosphonate followed by reduction of the resulting diphosphonate gives a new branched phosphine, bis(3-phosphinopropyl)phenylphosphine. Its reaction with paraform and p-toluidine yields oligomeric 3-[3-(propylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3,7-diazadiphosphacyclooctane. Diethyl (5-allyl-2-ethoxybenzyl)phosphonate was obtained. Its reduction gives unsaturated (5-allyl-2-ethoxybenzyl)phosphine. This product adds two moles of formaldehyde to give bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine. The reaction of this compound with p-toluidine yielded, depending on the conditions, the corresponding bis(aminomethyl)phosphine, 1,3,5-diazaphosphorinane, and 1,5,3,7-diazadiphosphacyclooctane, and also their derivatives containing allyl substituents.

Optically Active Cage P,N-Containing Cyclophanes Based on L-Menthylphosphine and Their Platinum (II) and Palladium (II) Complexes

Abstract We report here a synthesis of novel chiral P,N-containing cyclophanes with l-menthyl substituents on the phosphorus atoms and their platinum (II) and palladium (II) complexes.