Organonickel σ-Complexes—Key Intermediates of Electrocatalytic Cycles

Electrochemical reduction of nickel complexes with 2,2-bipyridyl in the presence of ortho-substituted aromatic bromides or white phosphorus leads to the formation of highly reactive organonickel -complexes that are capable of selectively reacting with diverse substrates with the formation of cross-association products. Mechanisms of electrocatalytic processes involving organic halides, chlorophosphines, white phosphorus, and nickel complexes with 2,2-bipyridyl are studied by the cyclic voltammetry and preparative electrolysis methods. Key intermediates of processes that occur in metallocomplex catalysis are determined.     

Synthesis and molecular structure of 3,7-dimethyl-2-[N-(4-methylpyridyl-2)-4-hydroxy-3-methyl-5-oxopyrrolen-3-yl-2]imidazo[1,2-a]pyridine

Heterocyclization of 2-chloroepoxy-1,1-diethoxy-2.3-butane with 2-amino-4-methylpyridine occurred with participation of all three potential electrophilic centers to give 3,7-dimethyl-2-[N-(4-methylpyridyl-2)-4-hydroxy-3-methyl-5-oxopyrrolen-3-yl]imidazo[1,2-a]pyridine, the structure of which was determined by X-ray crystallography. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1089–1094, July 2006.     

Electrochemical reduction of cobalt and nickel complexes with ligands stabilizing metal in low oxidation state

Electrochemical reduction of cobalt(ii) complexes containing -acceptor ligands (L = bpy, Ph₂Ppy) proceeds through three consecutive reversible steps: one-electron transfer to form a more stable Co^IL complex, transfer of two electrons at more negative potentials to form an anionic [NiL]^– complex, and reduction of the ligand to the radical anion. The stability of the cobalt complexes with different ligands decreases in the series Ph₂Ppy > Ph₃P > bpy.     

Synthesis of new macrocyclic aminomethylphosphines based on 4,4"-diaminodiphenylmethane and its derivatives

The reaction of bis(hydroxymethyl)phenylphosphine with 4,4"-diaminodiphenylmethane in DMF afforded 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis. Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2 and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of bis(hydroxymethyl)phenylphosphine with bis(4-N-methylaminophenyl)methane in DMF followed by sulfurization yielded monocyclic bis{methylenedi[p-phenylene(N-methyl)aminomethyl]}di(P-phenyl)phosphine sulfide (4).     

Electrochemical approaches to generation of phosphinidene complexes of tungsten pentacarbonyl

An alternative approach to synthesis of electrophilic terminal phosphinidene complexes of tungsten pentacarbonyl with various substituents at the phosphorus atom has been developed. The approach is based on the reaction of the electrochemically generated tungsten pentacarbonyl ion with trivalent phosphorus acyl chlorides. Electrochemical reduction of ethyldichlorophosphines in the presence of α-diimines is a one-step process that forms 1,3,2-diazaphospholenes containing an exocyclic P-C bond.     

New aminomethylphosphines with cyanophenyl substituents at the nitrogen atoms

A condensation of bis(hydroxymethyl)arylphosphines with 3- and 4-aminobenzonitriles leads to the corresponding 3,7-diaryl-1,5-bis(cyanophenyl)-1,5-diaza-3,7-diphosphacyclooctanes. Acyclic (aryl)bis[N-(2-cyanophenyl)aminomethyl]phosphines are formed in the case of 2-aminobenzonitrile. Molecular and crystalline structure of the compounds obtained was studied by X-ray diffraction analysis.     

α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

1. Download : Download high-res image (40KB)
2. Download : Download full-size image

     

Synthesis and Structure of the Heterocyclic Phosphorus Containing Derivatives of [60] Fullerene

Abstract

Data on the structure of cycloadducts of organophosphorus dipolar reagents and fullerenes arc absent, to our knowledge. We died the reactions and the shucturc of cycloadducts of phosphorylated azidcs and nitrile oxide with [60]fullcrcnc. The cycloaddition of diphcnylphosphinic llzide to fullcrme has bcm determined to lead to the 1 -[(N-diphenylphosphoryl)amino]-2-hydroxy[6O]hllcrme (l), the mixhuc of phosphorylated aziridinofullcrcne (2) and derivative of fullerne (3) with one aziridine fragment and one aminohydmxy-fragment, or to product (4), depending on the conditions of don .