Transfer of the chelating ligands in the systems [LAuCl2]+-[PdCl4]2−: Synthesis and structure of the salt (NH4)0.20[(Bipy)AuCl2]1.04[(Bipy)PdCl2]0.96[AuCl4]0.76[PdCl4]0.24

The formation of binary complex salts containing gold(III) in the cation and palladium(II) in the anion in the systems [(Bipy)AuCl₂]⁺-[PdCl₄]^2? occurs by transfer of the N,N-electron-donating chelating ligand bipyridine and the chloride ligands between the gold-containing cation and the palladium-containing anion. The resulting neutral salt [(Bipy)PdCl₂] crystallizes together with the anion [AuCl₄]^? from acetonitrile-water (1 : 1-1 : 2, v/v) to give the complex salt (NH ₄ ⁺ )_0.20[(Bipy)AuCl ₂ ⁺ ]_1.04[(Bipy)PdCl₂]_0.96[AuCl ₄ ^? ]_0.76PdCl ₄ ^2? ]_0.24 with a total Au : Pd ratio of 3 : 2. The ammonium cation is formed from acetonitrile upon its hydrolysis most likely catalyzed by Pd complexes. Quantum-chemical calculations were performed to study the transfer of the chelating ligand theoretically.     

Distribution of ligands in polynuclear palladium complexes: DFT study of isomerism of Pd4(L)4(RCO2)4 (L = CO,CH2, NO) complexes

Structural isomerism of the Pd₄(L)₄(RCO₂)₄ (L = CO, CH₂, NO; R = CC1₃, CF₃, CH₃) complexes was studied in the framework of the density functional theory (DFT). Among the Pd₄(CO)₄(RCO₂)₄ and Pd₄(CH₂)4(RCO₂)₄ complexes the most stable were the isomers with alternate coordination of pairs of carbonyl and carboxylate ligands on the sides of a planar rectangular metal core. The isomers with the pairwise coordination of NO/RCO₂ on one side of the metal core are the most stable between the Pd₄(NO)₄(RCO₂)₄ complexes. The features of mutual coordination of ligands in polynuclear complexes of palladium are clarified using the obtained results.

     

New Reaction of Dimethylformamide with Acrylic Acid

Russian Journal of Organic Chemistry - A new homogeneous reaction of dimethylformamide (DMF) with acrylic acid was studied. The reaction afforded previously unknown...     

Synthesis of Oligomers by Oxidative Dehydrogenation of Dihydric Phenols and Quinones with 3,3′,5,5′-Tetra-<Emphasis Type="Italic">tert</Emphasis>-butyl-<Emphasis Type="Italic">trans</Emphasis>-stilbenequinone

Oxidative dehydrogenation of pyrocatechol and 1,4-benzoquinone with 3,3′,5,5′-tetra-tert-butyl-trans-stilbenequinone as oxidant afforded oligomeric polyhydroquinones and polyquinones. Appropriate reaction conditions have been found, and the resulting oligomers have been characterized by IR and MALDI TOF mass spectra and elemental analyses.     

Synthesis,Transport, and Ionophoric Properties of α,ω-Biphosphorylated Azapodands: X. Membrane Transport of Organic Acids by Phosphorylated α,ω-Diazapodands

The membrane transport properties of novel phosphorylated azapodands with respect to mono- and polyfunctional carboxylic acids were studied. The structures of the transported Н-complexes are discussed, the complexing centers in the carriers are considered, and the correlations between the structure and transmembrane transport efficiency of the acid substrates are demonstrated.     

Unexpected participation of nucleophiles in the reaction of palladium(II) acetate with divalent 3<Emphasis Type="Italic">d</Emphasis> metals

The kinetics of reactions of palladium(II) acetate with cobalt(II), nickel(II), and copper(II) acetates were studied by spectrophotometry. These reactions produce heterobimetallic complexes Pd^II(μ-OOCMe)₄M^II(OH₂)(HOOCMe)₂, where M = Co, Ni, or Cu. These reactions are very slow in carefully dehydrated (<0.01% H₂O) acetic acid, but are considerably enhanced by water or acetonitrile. Our data indicate that the activation of the kinetically inert ring structure of the initial palladium complex Pd₃(μ-OOCMe)₆ by means of the nucleophilic attack of an H₂O or acetonitrile molecule is the key step of the reaction mechanism.     

Polymer Complexes and Their Flocculation Power

Complexation of various complementary polymers and the flocculating power of the resulting complexes were studied. Regression equations adequately describing the recovery of phenol by polymeric complex reagents are presented.     

Influence of the reagent pretreatment of wastewaters from chemical plants on the efficiency of their biological treatment

Russian Journal of Applied Chemistry - Structure formation in the flocculant-wastewater component system was studied by viscometry and IR spectroscopy. Statistical treatment of the experimental...     

Polymeric Heterogeneous Catalysts of Transition‐Metal Oxides: Surface Characterization,Physicomechanical Properties,and Catalytic Activity

We investigate the physicomechanical properties of polymeric heterogeneous catalysts of transition‐metal oxides, specifically, the specific surface area, elongation at break, breaking strength, specific electrical resistance, and volume resistivity. Digital microscopy, Fourier‐transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and energy‐dispersive analysis are used to study the surfaces of the catalysts. The experimental results show that polymeric heterogeneous catalysts of transition‐metal oxides exhibit high stability and can maintain their catalytic activity under extreme reaction conditions for long‐term use. The oxidation mechanism of sulfur‐containing compounds in the presence of polymeric heterogeneous catalysts of transition‐metal oxides is confirmed. Microstructural characterization of the catalysts is performed by using X‐ray computed tomography. The activity of various catalysts in the oxidation of sulfur‐containing compounds is determined. We demonstrate the potential application of polymeric heterogeneous catalysts of transition‐metal oxides in industrial wastewater treatment.     

New Synthesis of 3,3′,3″-Nitrilotripropionic Acid

Russian Journal of Organic Chemistry - A new procedure has been developed for the synthesis of 3,3′,3″-nitrilotripropionic acid (NTP) by reaction of formamide with acrylic acid in a...