Volume 89, Issue 3

The character of bis(2,4,6-tri- tert -butylphenyl)diphosphene is described experimentally and theoretically. The diphosphene is stabilized by steric protection and the structure can be characterized by spectroscopic as well as crystallographic analyses. Theoretical calculation on the diphosphene strongly suggests that the P=P bond is an isolated double bond and that the P–C bonds are single covalent bond. The reactivity has been investigated including photolysis, oxidation, sulfurization, selenation, transition-metal complex formation, and carbene addition. Plausible mechanistic scheme for the reaction of the diphosphene with 3,4,5,6-tetrachlorocyclohexa-3,5-diene-1,2-dione (or tetrachloro- o -benzoquinone) to a pentavalent spiro product is discussed based on the product analysis.

Some scientists believe today that problems related to phosphorus entry into fresh-water bodies may be more important for setting the planetary boundary. Excessive entry of biogenic elements (especially phosphorus) into water bodies and water streams causes their eutrophication. This process may cause a decrease in the light transmittance of surface water layers and other consequences for ecosystem and humans. In this paper the results of model application for the estimation of the phosphorus content in fresh waters of the Russian Federation regions are presented. The method for the estimation of the phosphorus amount in fresh water was developed on the basis of the dynamic model. Phosphorus loading is most characteristic of regions that have developed types of agriculture which cause increases the rate of mineral phosphorus entry into erodible soil.

Abstract: Rational design of title ligands and their transition metal complexes gave the high effective catalysts for hydrogen economy and perspective “stimuli-responsive” luminescent materials. Together with the above novel cyclic aminomehtylphospine ligands have showed a row of unpredicted properties like spontaneous formation of macrocyclic molecules, unique reversible slitting of macrocycles on to the smaller cycles, rapid interconversion of the isomers catalyzed by both acids and transitional metals, bridging behavior of usually chelating ligands and unexpected high influence of handling substituents on N-atoms on to the catalytic and luminescent properties of P-complexes.

The development of practical, efficient and atom-economical methods of formation of carbon-phosphorus bonds remains a topic of considerable interest for the current synthetic organic chemistry and electrochemistry. This review summarizes selected topics from the recent publications with particular emphasis on phosphine and phosphine oxides formation from white phosphorus, chlorophosphines in electrocatalytic processes using aryl, hetaryl or perfluoroalkyl halides as reagents. This review includes selected highlights concerning recent progress in modification of catalytic systems for aromatic C–H bonds phosphonation involving metal-catalyzed ligand directed or metal-induced oxidative processes. Furthermore, a part of this review is devoted to phosphorylation of olefins with white phosphorus under reductive conditions in water-organic media. Finally, we have also documented recent advances in ferrocene C–H activation and phosphorylation.

A series of mono-, di- and tetranuclear copper(I) complexes with macrocyclic 14-, 16-, 18- and 20-membered tetrakis-phosphine ligands (P 4 N 2 ) was obtained and fully characterized including single crystal X-ray diffraction. The 14-membered P 4 N 2 macrocycles form very stable cationic mononuclear tetraphospha-coordinated copper(I) complexes, whereas their higher 16-, 18- and 20-membered homologues give neutral dinuclear [Cu 2 I 2 L] complexes under the same conditions. An unusual tetranuclear complex with two three- and two four-coordinated copper(I) atoms was obtained from 16-P Mes 4 N CH2CH2Py-2 2 and copper(I) iodide. This is the first example of N-coordination of cyclic aminomethylphosphines towards “soft” copper(I).

In this paper, we report on the different synthetic strategies which led to the preparation of a whole family of polyaromatic hydrocarbons containing a P-atom at the edge. In particular, we show from both experimental and theoretical perspective how the Scholl method has to be adapted to the specificity of organophosphorus derivatives. The P-modified PAHs possess the classical phosphane reactivity that allows fine-tuning of their electronic properties as evidenced by spectro-electrochemistry and theoretical calculations. In particular, the effect of P-substitution on the aromaticity of the different cycles of the PAH was studied.

This account outlines the recent results on our strategy of the diastereoselective asymmetric synthesis of aminophosphonic acids (APs) using enantiomeric sulfinimines as chirality inducing reagents. Three important topics are discussed: (a) application of a double asymmetric induction in the synthesis of enantiomerically pure APs; (b) development of a general approach to the synthesis of γ-aminophosphonic acids (γ-APs) and (c) the use enantiomeric N- ( p -tolylsulfinyl)cinnamaldimines in the synthesis of diverse α- and β-aminophosphonic acids (AP3, AP4) including the first synthesis of ( R )-phosphoemeriamine.

In this paper, we review some of our results on cycloaddition and cyclization reactions of allenylphosphonates/and allenyl phosphine oxides. Thus nitro-substituted propargylic alcohols react with P(III)–Cl substrates to lead to unprecedented phosphono-benzazepines or -hydroxyindolinones. A similar reaction using a higher stoichiometry of P(III)–Cl precursor has led to the first observation of spontaneous resolution by crystallization in allene chemistry. In the reaction of these phosphorus based allenes with diphenyl isobenzofuran (DPBF), depending on the substituents, both [α, β] and [β, γ]-cycloaddition products are formed. Extension of this work to sulfur based allenes and leading to a new [4+2] cycloadduct with DPBF is reported. A novel cyclization reaction of a functionalized allenylphosphine oxide with diethylamine leading to 3-diethylamino-4-diphenylphosphinoyl-1-naphthol is discovered. Base-catalyzed reactions of allenylphosphonates with 2-substituted benzaldehdes lead to novel thiochromans, chromenes, and quinolines. Allenylphosphonates undergo phosphonylation in the presence of tetrabutyl ammonium fluoride (TBAF). Vinyl azides derived from allenylphosphonates undergo thermolysis to form bis-phosphonopyrazines. [Pd]-catalyzed reactions of allenes with 2-iodophenols, 2-iodobenzyl alcohol and 3-iodo-indole-2-carboxylic acids lead to a variety of benzofurans, benzopyrans and benzopyranones, respectively.

This contribution is a documentation of recent advances in the chemistry of chalcogenide polynuclear transition metal complexes coordinated with mono- and di-phosphines functionalized with hydroxo groups. A survey of complexes containing tris(hydroxymethyl)phosphine (THP) is presented. The influence of the alkyl chain in bidentate phosphines, bearing the P–(CH 2 ) x –OH arms, is also analyzed. Finally, isolation and structure elucidation of the complexes with HP(OH) 2 , P(OH) 3 , As(OH) 3 , PhP(OH) 2 , stabilized by coordination to Ni(0) and Pd(0) centers embedded into chalcogenide clusters, is discussed.

Conformational analysis of derivatives of bis(2-phenylethyl)selenophosphinic acid was carried out by the method of dipole moments and density functional theory calculations. The conformations of the examined compounds fit into the overall conformational picture for the PIV compounds: these derivatives exist as conformational equilibrium of non-eclipsed gauche and trans forms with propeller arrangement of the substituents relative to the P=Se bond. We stipulate that the eclipsed cis orientation of substituent may be caused by the formation of H-contact.