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© 2017, Springer Science+Business Media, LLC, part of Springer Nature. N-Heterocyclic carbenes (NHCs) are widely used as ligands in catalysis by transition metal complexes. The catalytic activity of transition metal NHC complexes is much higher than that of the transition metal complexes bearing the phosphine and nitrogen-containing ligands. They show excellent catalytic performance in different transformations of the organic compounds, especially in the carbon—carbon and carbon—element bond forming reactions. Palladium NHC complexes are very efficient catalysts for the cross-coupling reactions. On the other hand, nickel is less expensive and regarded as a promising alternative to palladium and, therefore, it attracts increasing attention from the researches. The present review is focused on the recent advances in the synthesis of N-heterocyclic carbene complexes of nickel and palladium and their application in catalysis of cross-coupling reactions of organic, organoelement and organometallic compounds with organic halides.

© 2017 IUPAC & De Gruyter. The new efficient and environmentally safe methods for preparation of various classes of organic and organoelement compounds, including organonickel sigma-complexes and organophosphorus compounds bearing P-C bonds have been created using the electrochemical methods. The synthetic application of the elaborated techniques towards the process of formation of new carbon-carbon, carbon-metal and carbon-phosphorus bonds are discussed. The mechanisms of the proposed processes and the nature of the formed in the overall electrochemical process intermediates are disclosed. The elaborated methods operated in the principals of "green chemistry" can be considered as an efficient alternative to some classical methods for preparation of active catalysts, biologically active molecules and new polynuclear complexes displaying practically useful properties.

© 2017 Elsevier B.V.The work introduces Tb(III)-centered luminescence of amino-modified silica nanoparticles doped with Tb(III) complexes for cellular imaging. For these purposes water-in-oil procedure was optimized for synthesis of 20 and 35 nm luminescent nanoparticles with amino-groups embedded on the surface. The obtained results indicate an impact of the nanoparticle size in decoration, aggregation behavior and luminescent properties of the nanoparticles in protein-based buffer solutions. Formation of a protein-based corona on the nanoparticles surface was revealed through the effect of the nanoparticles on helical superstructure of BSA. This effect is evident from CD spectral data, while no any size impact on the adsorption of BSA onto aminomodified silica surface was observed. Cellular uptake of the nanoparticles studied by confocal and TEM microscopy methods indicates greater cellular uptake for the smaller nanoparticles. Cytotoxicity of the nanoparticles was found to agree well with their cellular uptake behavior, which in turn was found to be greater for the smaller nanoparticles.

© 2017 Elsevier B.V.Cationic palladium complexes stabilized by a tridentate neutral (N,N,C) ligand containing a sterically hindered N-heterocyclic carbene (NHC) moiety have been prepared and characterized. The nature of the anionic counterion in the palladium complex has been varied to get crystals suitable for X-ray diffraction. The square planar structure of one of these complexes along with the axial contribution of the sterically hindered NHC fragment has been confirmed by X-ray analysis. In addition, all the isolated [(κ3-N,N,C)PdIICl]+X- [X- =Cl, PF6, BF4, B(C6H3Cl2)4] ion pairs have been scrutinized as catalysts in the cross-coupling Suzuki-Miyaura reaction between phenylboronic acid and variably substituted halo-aryl acceptors. Selected issues from this series have shown improved catalyst turn-over frequencies (TOFs) with respect to structurally related catalytic systems of the state-of-the-art.

© 2017, Springer Science+Business Media, LLC. One-dimensional coordination polymer was obtained by cation exchange reaction of triethylammonium salt of methyl ent-16α-H-phosphonyloxybeyeran-19-oate with CuCl 2 . Its structure was determined by single crystal X-ray diffraction analysis. The formation of hydrophilic channels consisting of phosphorus containing fragments, copper atoms, and water, which are framed by hydrophobic surroundings from tetracyclic bulky beyeran substituents, is observed in the crystal. The study of the temperature dependence of the static magnetic susceptibility of the polymer indicates a weak antiferromagnetic interaction between the copper spins.

© 2017 Elsevier LtdThe formation of binuclear nickel complexes of type [Ni2(µ-O2PR1R2)2(bpy)4]Br2, where R1 = H, R2 = phenyl (Ph), 2,4,6-trimethylphenyl (Mes), 2,4,6-triisopropylphenyl (Tipp) or R1R2 = [sbnd]OCH2CH(Et)NHCH(Ph)[sbnd]; bpy = 2,2′-bipyridine, in solution and their fragmentation behavior have been investigated by ESI and MALDI mass spectrometry. It was found that binuclear cationic fragments [Ni2(µ-O2PR1R2)2(bpy)2Br]+ are characteristic ions displaying the formation of binuclear nickel(II) complexes in solution.

© 2017 American Chemical Society.Solid lipid nanoparticles (SLNs) are among the most promising nanocarriers to target the blood-brain barrier (BBB) for drug delivery to the central nervous system (CNS). Encapsulation of the acetylcholinesterase reactivator, pralidoxime chloride (2-PAM), in SLNs appears to be a suitable strategy for protection against poisoning by organophosphorus agents (OPs) and postexposure treatment. 2-PAM-loaded SLNs were developed for brain targeting and delivery via intravenous (iv) administration. 2-PAM-SLNs displayed a high 2-PAM encapsulation efficiency (∼90%) and loading capacity (maximum 30.8 ± 1%). Drug-loaded particles had a mean hydrodynamic diameter close to 100 nm and high negative zeta potential (-54 to -15 mV). These properties contribute to improve long-term stability of 2-PAM-SLNs when stored both at room temperature (22 °C) and at 4 °C, as well as to longer circulation time in the bloodstream compared to free 2-PAM. Paraoxon-poisoned rats (2 × LD50) were treated with 2-PAM-loaded SLNs at a dose of 2-PAM of 5 mg/kg. 2-PAM-SLNs reactivated 15% of brain AChE activity. Our results confirm the potential use of SLNs loaded with positively charged oximes as a medical countermeasure both for protection against OPs poisoning and for postexposure treatment.

© 2017, Springer Science+Business Media, LLC. The reactivity of organonickel sigma-complexes of type [NiBr(Ar)(bpy)], where Ar = 2,6-dimethylphenyl (Xyl), 2,4,6-trimethylphenyl (Mes), 2,4,6-triisopropylphenyl (Tipp), 2,4,6-tricyclohexylphenyl (Tchp), bpy = 2,2´-bipyridine, towards nitriles (acetonitrile, propionitrile, chloroacetonitrile, benzonitrile) has been investigated. This reaction leads to imines by formation of new carbon—carbon bond between aromatic fragment and nitrile group C≡N.

© 2017, Springer Science+Business Media, LLC, part of Springer Nature. N-Heterocyclic carbenes (NHCs) are widely used as ligands in catalysis by transition metal complexes. The catalytic activity of transition metal NHC complexes is much higher than that of the transition metal complexes bearing the phosphine and nitrogen-containing ligands. They show excellent catalytic performance in different transformations of the organic compounds, especially in the carbon—carbon and carbon—element bond forming reactions. Palladium NHC complexes are very efficient catalysts for the cross-coupling reactions. On the other hand, nickel is less expensive and regarded as a promising alternative to palladium and, therefore, it attracts increasing attention from the researches. The present review is focused on the recent advances in the synthesis of N-heterocyclic carbene complexes of nickel and palladium and their application in catalysis of cross-coupling reactions of organic, organoelement and organometallic compounds with organic halides.

© 2015 Elsevier B.V. This work highlights the H-function of Tb(III)-doped silica nanoparticles in aqueous solutions of acetic acid as a route to sense acetylcholinesterase-catalyzed hydrolysis of acetylcholine (ACh). The H-function results from H+-induced quenching of Tb(III)-centered luminescence due to protonation of Tb(III) complexes located close to silica/water interface. The H-function can be turned on/switched off by the concentration of complexes within core or nanoparticle shell zones, by the silica surface decoration and adsorption of both organic and inorganic cations on silica surface. Results indicate the optimal synthetic procedure for making nanoparticles capable of sensing acetic acid produced by enzymatic hydrolysis of acetylcholine. The H-function of nanoparticles was determined at various concentrations of ACh and AChE. The measurements show experimental conditions for fitting the H-function to Michaelis-Menten kinetics. Results confirm that reliable fluorescent monitoring AChE-catalyzed hydrolysis of ACh is possible through the H-function properties of Tb(III)-doped silica nanoparticles.

© 2015 Elsevier B.V. The biomimetic nature of micellar catalysis can significantly affect the rate of chemical reactions due to the effects of concentration and the change of microenvironment. Here, a key role is played by the nature of the head group. The catalytic activity of alkyltriphenylphosphonium bromides (TPPB-n; n= 10, 12, 14, 16, 18; n is the number of carbon atoms in alkyl groups) in the nucleophilic substitution of p-nitrophenyl esters of alkylchloromethylphosphonic acid were investigated by the method of spectrophotometry. Using pyrene, prodan and Sudan I as probes the values of critical micelle concentrations and aggregation numbers were determined. A comparison of the results of kinetic dependence processing by Berezin equation obtained for TPPB series with the known ammonium analogues was carried out. It was found that for TPPB- n series, the higher acceleration of reaction has been achieved due to concentration factor compared to ammonium surfactants. This agrees with the fact that alkyltriphenylphosphonium bromides demonstrate higher aggregation activity forming micelles with higher solubilizing capacity.

© 2016 Taylor & Francis Group, LLC.The reactivity of organonickel sigma-complex [NiBr(Mes)(bpy)], where Mes = 2,4,6-trimethylphenyl, bpy = 2,2’-bipyridine towards phenylphosphine (PhPH2) has been investigated. It was found that this interaction leads to secondary mesitylphenylphosphine and dimesitylphosphine by formation of new carbon-phosphorus bond involving mesityl fragment of starting organonickel sigma-complex.

© 2016 Taylor & Francis Group, LLC.We present the study of reactivity of electrochemically generated in situ from white phosphorus P4 phosphine oxide H3PO toward various ketones (acetone, methylethylketone, methyl-n-propylketone). This interaction was found to give a selective formation of mono- and bis-(α-oxyalkyl)phosphine oxides RRʹC(OH)P(O)H2 (1) and (RRʹC(OH))2P(O)H (2) where R = Me; Rʹ = Me, Et, n-Pr. Thermal properties of the formed primary and secondary phosphine oxides have been studied and quantum chemical calculations of thermodynamic stability of these compounds were performed.

© The Royal Society of Chemistry. A series of diverse binuclear and mononuclear cyclometalated palladium(ii) complexes of different structure was investigated by electrochemical techniques combined with density functional theory (DFT) calculations. The studies including cyclic and differential pulse voltammetry, X-ray structure analysis and quantum chemical calculations revealed a regularity of the complexes oxidation potential on the metal-metal distance in the complexes: the larger Pd-Pd distance, the higher oxidation potentials. The reduction potentials feature unusually high negative values while no correlation depending on the structure could be observed. These results are in a good agreement with the electron density distribution in the complexes. Additionally, ESR data obtained for the complexes upon oxidation is reported.

© 2016 The Royal Society of Chemistry.The present work describes a new method to sense cholinesterase-catalyzed hydrolysis of acetylcholine (ACh) through a luminescence response of the hexarhenium cluster complex [{Re6S8}(OH)6]4-. A proton released from acetylcholinesterase (AChE)- or butyrylcholinesterase (BuChE)-catalyzed hydrolysis of ACh results in time-resolved sensitization of cluster-centered luminescence. The sensitization results from protonation of apical hydroxo-groups of the cluster complex. The protonation is affected by a counter ion effect. Thus, optimal conditions for adequate sensing of acetic acid produced by ACh hydrolysis are highlighted. Time-resolved luminescence and pH measurements under conditions of AChE-catalyzed hydrolysis of ACh show a good correlation between the cluster-centered luminescence and pH-induced inhibition of AChE. The inhibition is not significant within the first two minutes of ACh hydrolysis. Thus, the luminescence response measured within two minutes is dependent on both substrate and enzyme concentrations, which fits with AChE and BuChE kinetics. The usability of cluster-centered luminescence for monitoring the concentration-dependent inhibition of AChE with irreversible inhibitors is demonstrated, using a carbamylating agent, pyridostigmine bromide, as a model.

© 2016 Elsevier B.V. All rights reserved. A new crystalline polymorph of known chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) complex [RuCl(PPh3)2(η5-C5H5)] was obtained and characterized by various analytical methods including single-crystal and powder X-ray diffraction (XRPD) and differential scanning calorimetry (DSC) in combination with thermo-gravimetric analysis (TG-DSC). The obtained crystals of new polymorph are monoclinic, space group P21/n, with a = 11.125(4), b = 19.184(6), c = 15.946(5) Å, α = 90, β = 100.174(5), γ = 90, and Z = 4. It has been found that real melting point of the complex (M.p. = 252-253 °C) can be determined only in inert atmosphere while an apparent melting is observed in the range 142-150 °C due oxygen promoted oxidative dissociation of triphenylphosphine ligand.

© 2016 Mendeleev Communications. Published by ELSEVIER B.V.The electrochemical reduction of [NiBr2(bpy)] (bpy is 2,2'-bipyridine) complex in the presence of 2,4,6-tricyclohexylphenylbromide (TchpBr) in undivided electrochemical cell supplied with a sacrificial nickel anode results in the one-pot formation of an organonickel complex [NiBr(Tchp)(bpy)] bearing three cyclic substituents in the s-bonded aromatic ring. The synthesized complex was characterized by various methods including single crystal X-ray analysis.

© 2016 American Chemical Society.A flexible and hydrolytically stable metal-organic framework [Mn(H2O)2(Fc(PHOO)2)·2H2O]n has been synthesized using ferrocene-based ligand bearing phosphinic groups (Fc(PHOOH)2 = 1,1′-ferrocenediyl-bis(H-phosphinic acid)). In this compound manganese atoms are bound by phosphinate fragments to give infinite chains, and the latter are interconnected by ferrocene groups to form two-dimensional coordination polymer. The elimination of both coordinated and lattice water molecules during heating up to 150 °C produced the compound, which is nonporous for nitrogen, but can selectively adsorb water over methanol and other solvents at 298 K. The reversible structural transformation during adsorption/desorption of water is also reflected in a change of magnetic properties of the metal-organic framework.

© 2015 Elsevier B.V. All rights reserved. The two new nickel complexes [Ni(PR2NPh(CH)Ph2)2]2+ (where R = Ph or o-Py) with cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been synthesized. All complexes are effective electrocatalysts for hydrogen production using [(DMF)H]+ as proton source in acetonitrile. The bulky benzhydryl substituent at nitrogen atom leads to higher catalytic activity comparison to benzyl. The introduction o-Py substituents at phosphorus as additional basic center is caused by the changing of voltage-current picture and significantly catalytic current enhancement. TOFs being 100 and 15200 s-1 for R = Ph and o-Py, respectively.

© 2015, Pleiades Publishing, Ltd. Electrochemical properties of the [NiBr2(bpy)2] complex, where bpy = 2,2′-bipyridyl, have been studied in the presence of derivatives of ortho-phosphine phenol: 2-diphenyl phosphanyl-4-methyl phenol CH3C6H3(PPh2)OH (1), 2-diphenyl phosphanyl-4-methylphenyldiphenyl phosphinate CH3C6H3(PPh2)OP(O)Ph2 (2), and 2-diphenylphosphoryl-4-methyl phenol CH3C6H3(P(O)Ph2)OH (3). It is found that interaction of products of electrochemical reduction of complex [NiBr2(bpy)2] with 1 and 2 results in formation of active catalysts of the process of homogeneous oligomerization/polymerization of ethylene.

© The Royal Society of Chemistry 2015. Ni-catalyzed electroreductive olefin perfluoroalkylation affords both monomeric and dimeric products depending on the reaction media. Recycling of the catalyst can be achieved by immobilization of a (bpy)NiBr2 complex on silica nanoparticles decorated with anchoring amino-groups. Switching the homogeneous and heterogeneous catalysts is found to be one more factor to control the product ratio. This catalytic technique is both green and atom economical and combines the advantages of nanoheterogeneous catalysis and electrocatalysis.

© 2015 Mendeleev Communications. Published by Elsevier B.V. The reaction of cobalt dibromide hexahydrate with 2,2′-bipyridine (bpy) and 9-anthrylphosphinic acid AntP(O)(OH)H (Ant = 9-anthryl) leads to the first example of a neutral dinuclear cobalt(ii) complex {Co2Br2[μ-O2P(H)Ant]2(bpy)2} formed by two bridging [μ-O2P(H)Ant]- ligands. The complex has been characterized by X-ray diffraction analysis and quantum-chemical calculations.

© 2015, Pleiades Publishing, Ltd. Electrochemical properties and reactivity of electrochemically activated forms of organonickel sigma-complex [NiBr(Mes)(bpy)] (where Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine) were studied. The activation of the organonickel sigma-complex was found to proceed under both electrochemical reduction and oxidation conditions to give coordinatively unsaturated forms of the complex: radical [Ni(Mes)(bpy)]• and cationic complex [Ni(Mes)(bpy)]+, respectively. It was shown experimentally that the active forms of organonickel complex [NiBr(Mes)(bpy)] can react with organic substrates (cyclohexene, octene-1, tetrahydrofuran) and convert nitriles (acetonitrile, acetonitrile-d3, chloroacetonitrile) into corresponding imines containing 2,4,6-trimethylphenyl fragment.

The highest yields of phosphane oxide in the title process were obtained in electrochemical cells supplied with aluminium (49%), tin (36%) or zinc (67%) anodes.

© 2014 American Chemical Society. The organonickel complexes are organometallic compounds containing a Ni - C σ-bond (σ-complexes). These species are very reactive and have been mainly characterized as the intermediates of catalytic processes of cross coupling and homocoupling involving organic and elementoorganic substrates such as organic halides, chlorophosphines, unsaturated hydrocarbons, etc. Thus, only a limited number of these complexes have been isolated and characterized as the free stable species. Although the organonickel complexes have been known since the 1960s, the chemistry of these species is currently at the beginning stages of development. The interest of the researchers in this class of compounds has significantly increased over the past decade, resulting in a plethora of scientific papers published on this topic. At the same time, electrochemical methods have become more and more popular in modern synthetic chemistry, due to easy access to high reactive intermediates, including organometallic species, which can be selectively generated in situ and used for subsequent synthetic processes. This review summarizes the elaborated electrochemical approaches for the preparation of organonickel complexes, including a discussion of the important role of the electrochemical cell construction and the influence of the electrode material nature on the electrochemical process. In order to give more insight into the importance of organonickel complexes in synthetic chemistry and introduce the reader to this problem of organometallic chemistry, focused on the development of new synthetic protocols for preparation of stable organonickel complexes, an overview of the most important catalytic processes proceeding with participation of these highly reactive intermediates and the main types of organonickel complexes are presented. However, in this review organonickel complexes will be limited by examples in which the organic fragment is singly bonded to the nickel center, because these species are responsible for the catalytic reactions.

The organonickel complex [NiBr(Mes)(phen)] (1) (Mes = 2,4,6- trimethylphenyl, phen = 1,10-phenanthroline) was synthesized by oxidative addition of MesBr to nickel(0) complexes, obtained from [Ni(COD)2] (COD = 1,5-cyclooctadiene) and phen, or electrochemically generated from [NiBr2(phen)], and by ligand exchange reaction from [NiBr(Mes)(PPh3)2]. The electrochemical properties of [NiBr(Mes)(phen)] were investigated by cyclic voltammetry and in situ EPR spectroelectrochemistry. The cathodic reduction of 1 resulted in formation of the neutral radical complex [Ni(Mes)(phen-)] with a 1,10-phenanthroline radical anion bound to a nickel(II) centre. The electrochemical generation of the free 1,10-phenanthroline radical anion from 1,10-phenanthroline is also described. © 2013 Elsevier B.V. All rights reserved.

© 2014 Springer Science+Business Media New York. The influence of the aggregation properties of the medium on the catalytic activity of palladium nanoparticles stabilized by amphiphilic phosphonium salts was demonstrated for the Suzuki coupling of bromoarenes and phenylboronic acid.

New phosphorylated aminoacetal has been synthesized by the Kabachnik-Fields reaction; its reactivity has been studied in acid-catalyzed condensation with linear polyphenols (2-methylresorcinol, resorcinol, pyrogallol) and the Mannich reaction with macrocyclic polyphenol (calix[4]resorcinol). It has been determined for the first time that acid-catalyzed reaction of phosphorus-containing acetal with resorcinol and its derivatives in ethanol in the presence of hydrochloric acid gives new phosphorylated piperazines in addition to the compounds of diarylmethane series. Condensation of macrocyclic polyphenol (calix[4]resorcinol) with formaldehyde and N-((dihexylphosphoryl) methyl)-2, 2-dimethoxyethylamine (the Mannich reaction) has resulted in novel tetrasubstituted calixarene containing aminophosphine oxide and acetal groups on the "upper rim" of molecule. © 2014 Wiley Periodicals, Inc.

Novel ammonium salts of O,O-dialkyl dithiophosphoric acids were obtained by one-pot synthesis from white phosphorus, elemental sulfur, industrial alcohols or phenols, and amines. Long-chain S-alkyl O,O-dialkyldithiophosphonates were prepared by the reaction of red phosphorus with elemental sulfur, alcohols, and the cheap industrial fractions of C16-C18 and C 20-C26 of higher α-olefins in the presence of Lewis acid catalyst. The dithiophosphates obtained possess the high anticorrosion activities toward mild steel. © 2013 Copyright Taylor and Francis Group, LLC.

The reactivity of organonickel σ-complexes of the type [NiBr(Ar)(bpy)] (Ar is 2,4,6-tri-methylphenyl (Mes) or 2,4,6-triisopropylphenyl (Tipp); bpy is 2,2′-bipyridine) toward elemental (white) phosphorus was studied. For the reaction to occur, the complexes must be activated by removal of the bromide anion from the coordination sphere of nickel. This can be achieved either in the presence of halogen scavengers or by electrochemical reduction. The arylphosphinic acids ArP(O)(OH)H formed by hydrolysis of organic nickel phosphides are the major reaction products of the overall process. © 2013 Springer Science+Business Media New York.

The reaction of cobalt dibromide hexahydrate with 2,2'-bipyridine (bpy) and mesitylphosphinic acid MesP(O)(OH)H (Mes = = 2,4,6-trimethylphenyl) under solvothermal synthesis conditions leads to a new dinuclear cobalt(ii) complex {Co2[μ-O2P(H)Mes]2- (bpy) 4}Br2 formed by two bridging {μ-O2P(H)Mes}- ligands. X-ray crystal structure analysis of the complex displayed that cobalt ions have distorted octahedral coordination and are doubly bridged by two mesitylphosphinato ligands. © 2013 Mendeleev Communications. All rights reserved.

Electrochemical methods have become important from the viewpoint of the development and creation of new ecologically safe and resource-saving chemical processes. The use of electrons as a "universal" and "inexhaustible" reagent for chemical reactions is the main advantage of electrochemical tools. Although electrochemical processes have been already successfully applied in the preparation of different classes of practically important chemical compounds, a very limited number of industrially applicable electrochemical processes that involve elemental (white) phosphorus is currently known, except for some examples of the electrochemical production of phosphane PH3. These are mainly associated with the investigation of bulk reactions of the electrochemically activated P4 molecule and phosphorus intermediates derived therefrom; very limited attention has been paid to the electrode surface reactions as a key stage of the electrochemical process. In this Microreview we describe the electrode reactions of elemental (white) phosphorus and phosphane that accompany the electrochemical process of the preparation of some phosphorus compounds starting directly from P 4. The important role of the nature of the electrode material, the reactivity of the formed phosphorus intermediates and the surface processes are discussed. Moreover, recently, we succeeded in discovering a new, previously unstable phosphorus compound, phosphane oxide H3PO, which can be easily produced using an electrochemical method by mild anodic oxidation of phosphane PH3 electrochemically formed from P4. In this respect, some attention has been paid to the electrochemically induced processes of PH3 oxidation that result in the selective formation of phosphane oxide, which is of high interest from the viewpoint of the investigation of its properties and reactivity. Electrochemical processes involving elemental (white) phosphorus (P4) and phosphane (PH3) have been investigated and described. The importance of surface processes and the role of the electrode material in the electrochemical reactions have been elucidated. The electrochemical oxidation of PH3 and the generation of unstable H3PO using sacrificial metal anodes are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical methods have become important from the viewpoint of the development and creation of new ecologically safe and resource-saving chemical processes. The use of electrons as a "universal" and "inexhaustible" reagent for chemical reactions is the main advantage of electrochemical tools. Although electrochemical processes have been already successfully applied in the preparation of different classes of practically important chemical compounds, a very limited number of industrially applicable electrochemical processes that involve elemental (white) phosphorus is currently known, except for some examples of the electrochemical production of phosphane PH3. These are mainly associated with the investigation of bulk reactions of the electrochemically activated P4 molecule and phosphorus intermediates derived therefrom; very limited attention has been paid to the electrode surface reactions as a key stage of the electrochemical process. In this Microreview we describe the electrode reactions of elemental (white) phosphorus and phosphane that accompany the electrochemical process of the preparation of some phosphorus compounds starting directly from P 4. The important role of the nature of the electrode material, the reactivity of the formed phosphorus intermediates and the surface processes are discussed. Moreover, recently, we succeeded in discovering a new, previously unstable phosphorus compound, phosphane oxide H3PO, which can be easily produced using an electrochemical method by mild anodic oxidation of phosphane PH3 electrochemically formed from P4. In this respect, some attention has been paid to the electrochemically induced processes of PH3 oxidation that result in the selective formation of phosphane oxide, which is of high interest from the viewpoint of the investigation of its properties and reactivity. Electrochemical processes involving elemental (white) phosphorus (P4) and phosphane (PH3) have been investigated and described. The importance of surface processes and the role of the electrode material in the electrochemical reactions have been elucidated. The electrochemical oxidation of PH3 and the generation of unstable H3PO using sacrificial metal anodes are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The main electrochemical transformations of elemental (white) phosphorus were considered. Special attention was given to the recently developed processes of preparation of organophosphorus compounds (OPCs) with phosphorus-carbon bonds. The electrochemical approaches to the synthesis of OPCs from white phosphorus using organonickel and organozinc reagents are described. The importance of using the electrochemical methods for the generation of highly reactive phosphorus intermediates was shown for phosphine oxide H3PO obtained for the first time. This provides significant prospects for the electrochemical approaches that could be applied for the development of technologies of the chlorine-free synthesis of OPCs from white phosphorus. © 2012 Springer Science+Business Media New York.

The reaction of white phosphorus with the palladium(0) complex [Pd 2(dba)3] (dba is dibenzylideneacetone) leads to stable associates [Pd(P4)]n. The coordination polymer obtained is stabilized in a solid state via the formation of nanosized palladium phosphides Pd3P2 and Pd6P with average particle sizes of 140 and 65 nm, respectively. © 2011 Mendeleev Communications. All rights reserved.

n.a.

A reaction of bis(triphenylphosphine)palladium dibromide with white phosphorus in the presence of NaBPh4 selectively gives phosphorous acid H3PO3. The mechanism of the formation involves coordination of a white phosphorus molecule, ligand exchange, and hydrolysis of the coordinated P4 molecule in the coordination sphere of palladium. © 2010 Springer Science+Business Media, Inc.

Convenient synthetic route to prepare the germylene complexes of tungsten pentacarbonyls, W(CO)5{double bond, long}GeCl2 and W(CO)5{double bond, long}Ge{double bond, long}W(CO)5, electrochemically is developed. Combined quantum-chemical/IR spectroscopic approach is used for identification of the synthesized compounds. Good agreement between theoretical and experimental spectra can be regarded as one of the proofs of their supposed structures. © 2007 Elsevier B.V. All rights reserved.

The Raman spectra of different conformations of CH3SPCl 2, C2H5SPCl2, and (C 2H5S)2PCl are studied within the framework of the density functional theory (B3LYP/6-31G*and B3LYP/6-31+G*) using the method of scaling of force fields. Comparison of the calculated and experimental spectra makes it possible to interpret the latter and to establish the existence of trans and gauche conformers of these molecules, which are formed due to internal rotation about the P-S and S-C bonds. This comparison also shows that, for the prediction of the degrees of depolarization of Raman lines to be correct, it is necessary to introduce diffuse functions into the basis set. © Nauka/Interperiodica 2006.

The reviews covers authors" studies dealing with the synthesis of PIII- and PV-containing macrocycles and cryptands. The separation, structural characterization, and the chemical properties of a number of homeomorphic compounds with in,out bridgehead phosphorus atoms are described. Modification of the in-positions in macrobicyclic compounds with bulky groups is described for the first time.

The reviews covers authors" studies dealing with the synthesis of PIII- and PV-containing macrocycles and cryptands. The separation, structural characterization, and the chemical properties of a number of homeomorphic compounds with in,out bridgehead phosphorus atoms are described. Modification of the in-positions in macrobicyclic compounds with bulky groups is described for the first time.

The material of the sacrificial anode has a substantial effect on the nature and yield of the target products of electrochemical phosphorylation of organic halides by white phosphorus in the presence of the nickel complexes with 2,2′-bipyridine. The use of the zinc anode results in the products with tricoordinated phosphorus, viz., triorganylphosphines, the reaction on the aluminum anode affords triorganylphosphine oxides, and the presence of Mg 2+ ions in the reaction mixture provides the transformation of white phosphorus into cyclic phosphines (PhP)5.

A versatile method for the synthesis of tertiary phosphines with aromatic and heteroaromatic substituents by cross-coupling of chlorophosphines and organic halides catalysed by Ni0complexes of 2,2′-bipyridine was proposed.