Complexes [(1,2,4-Ph3C5H2)2NdCl2K(THF)2]2 (Nd1), {[1,2-Ph2-4-(4-MeOC6H4)C5H2]2NdCl2K(THF)2}2 (Nd2), {[1,2-Ph2-4-(2-MeOC6H4)C5H2]2NdCl2[K(THF)4]}(THF)0.5 (Nd3), and [(1,2,4-Ph3C5H2)2TbCl2K]2 (Tb1) have been synthesized, studied by X-ray diffraction analysis, and used in coordinative chain transfer polymerization (CCTP) of ethylene upon activation by alkyl magnesium derivatives. The complexes Nd1 and Tb1 exhibiting similar molecular structures and the same core type have demonstrated similar catalytic activities. Two types of alkylating/chain transfer agents, namely, di-n-butyl magnesium and heteroleptic complex (BHT)Mg(THF)2nBu Mg1 (BHT = 2,6-di-tert-butyl-4-methylphenoxide), have been studied in this reaction. We have found that (BHT)Mg(PE) products (PE is an oligoethylene chain) are being formed at a relatively high rate while using Mg1 at 40 °C in the solution polymerization of ethylene; the oligomeric products comprise more than 40 ethylene fragments, unlike Mg(PE)2 derivatives, which are obtained from MgnBu2 and contain about 20 ethylene fragments. Luminescence spectroscopy study of the reaction mixtures, while initiating the complex Tb1 by MgnBu2 or Mg1, confirmed the structural proximity and high symmetry of the catalytic complexes for both types of Mg reagents. These experimental results reaffirmed the hypothesis about the CCTP mechanism, suggesting the formation of trinuclear LnMg2 catalytic species. Within this mechanism, we can explain the increase in the polymerization degree (Pn) when Mg1 is used by growing a single oligoethylene chain (PE) per a Mg atom to form (μ-BHT)2Mg2(PE)2 species, whereas application of MgnBu2 provides the growth of two PE chains to form the Mg2(PE)4 product with lower solubility.

sized and structurally characterized. Their reaction with THF leads to the formation of the solvent-separated ion pairs [(Ph3CCOO)2Ln(THF)5]+[(Al(CH3)4]−. The tendency of the La3+ cation to interact with the π-electron system of phenyl rings has been revealed by molecular structure analysis for La-Al and Nd – Al tetramethylaluminate complexes in combination with the study of butadiene and isoprene polymerization by using catalyst system based on these complexes and aluminum alkyl cocatalysts. Coordination of Ln3+ cation by the π- electron conjugated system makes it difficult to form the catalytically active intermediates and decreases the catalytic activity.

A comparative study of various widely used methods of reductive amination is reported. Specifically, such reducing agents as H2, Pd/C, hydride reagents [NaBH4, NaBH3CN, NaBH(OAc)3], and CO/Rh2(OAc)4 system were considered. For understanding the selectivity and activity of the reducing agents reviewed herein, different classes of starting materials were tested, including aliphatic and aromatic amines, as well as aliphatic and aromatic aldehydes and ketones. Most important advantages and drawbacks of the methods, such as selectivity of the target amine formation and toxicity of the reducing agents were compared. Methods were also considered from the viewpoint of green chemistry.

Insulin internalization and intracellular insulin/receptor complex (IRC) processing provide with both the hormonal signal transduction elongation into cell and the dissociated complex parts utilization. The patterns of temperature influence on the insulin mechanism of action (IAM), in spite of a general opinion on temperature factor significance, have not been yet revealed. The results of the experimental studies previously carried out on four vertebrate classes isolated hepatocytes (lamprey, frogs, chickens, rats) and the data analysis have revealed the temperature factor particular effects on IAM separate stages in a family of vertebrates and clarified the number of important circumstances. 1- Some essential differentiations of insulin endo and exocytosis activity in poikilothermic and endothermic vertebrate hepatocytes have been found out. 2 - Besides, some significant changes of temperature influence on IAM in a cell have been revealed: a) At the 125 I-insulin internalization high level in cyclostomes (lamprey) hepatocytes the total absence of the process receptibility to temperature has been detected; b) The 125 I-insulin internalization receptibility to temperature at amphibians has been defined but only in the narrow range of low temperatures; c) The medium temperature changes show their influenced on 125 I-insulin internalization in endothermic cells (birds and mammals) within wide range (from 4-to 37ºC). 3 - Besides, the intracellular IRC processing crucial changes in different vertebrate classes hepatocytes have been determined: a) The 125 I-insulin molecule cytosolic degradation so as the 125 I-insulin exocytosis total absence have been revealed in lamprey cells; b) The lysosomal 125 I-insulin degradation takes place with hardly noticeable 125 I-insulin exocytosis in the frog cells; c) The abrupt increase of the degraded fragments portion in the total 125 I- insulin excreted fraction has been defined in chicken and especially in rat cells. Such changes are accompanied the increased temperature influence on the 125 I-insulin separate fractions exocytosis in rat hepatocytes. The data obtained allow us to trace three stages: 1) cyclostomes, 2) amphibians, 3) endothermic (birds, mammals), of temperature influence on 125 I-insulin internalization, and two stages of intracellular IRC processing temperature regulation as well in 1) amphibians, birds, as 2) in mammals. The results of the presented data analysis generally reflect insulin intracellular pathway alterations and hormone utilization during the vertebrata phylogenesis, so the temperature factor has a specific significance in phylogenesis as the selective IAM formation participant.

A new class of anthracene complexes with a metal coordinated at the central ring was applied in catalysis for the first time. As a result, a simple and efficient protocol for reductive amination that involves CO as a reducing agent has been developed. The rhodium complex [(cyclooctadiene)Rh(C10H4Me2(OMe)4)]+ (1 mol%) catalyses such reactions under mild conditions (40–130 °C) and produces a variety of amines in good yields (74–95%) without affecting the functional groups. The protocol is acceptable for all combinations of aldehydes (aromatic and aliphatic), ketones (aromatic and aliphatic) and amines (aromatic and aliphatic; primary and secondary).

A new protocol for the synthesis of nitriles from carbonyl compounds with elongation of the molecule with two carbon atoms was developed. It involves a reaction of ethyl cyanoacetate with different aldehydes in the presence of iron pentacarbonyl as a reducing agent. This protocol is very simple and requires only commonly available reagents, with no catalyst or complicated ligands being employed.

New hybrid bromobismuthates of 1,1'-(1,4-phenylenebis(methylene))bis(n-methylpyridin-1-ium) 1 (n=4) and 2 (n=3) dications and halobismuthates of 1-{[4-(Hal-methyl)phenyl]methyl}-2-methylpyridin-1-ium) 3 (Hal=Br) and 4 (Hal=I) monocations have been synthesized and characterized. The [BiBr5]2- anion with structure unusual for halobismuthates and two [BiBr6]3- anions form a linear 0-D fragment in compound 2. The Bi-Br(ax) distance in [BiBr5]2- anion (2.587 Å) is rather short for usual bromobismuthates. The formation of the linear fragment in compound 2 and the presence of short Bi-Br(ax) bonds in its structure do not affect a value of optical band gap.

Transition metal oxides are attractive noble metal-free catalysts of the oxygen reduction for application at the cathode of alkaline membrane fuel cells or metal-air batteries. However, despite of a rapidly increasing number of publications devoted to the oxygen electrocatalysis on transition metal oxides, a clear picture regarding the relations between their structure and composition on the one hand and electrocatalytic activity on the other hand is lacking. This short review discusses challenges facing researchers seeking to understand electrocatalysis of the oxygen reduction reaction on transition metal oxides.

Hydrothermal crystallization pathways of amorphous ceric phosphate gels were found to be determined by the ammonia concentration in a reaction medium. This allows for highly selective hydrothermal synthesis of various finely crystalline ceric phosphates, including Ce(PO4)(HPO4)0.5(H2O)0.5, (NH4)2Ce(PO4)2(H2O), and previously unknown NH4Ce2(PO4)3. The structure of the latter compound was solved from powder X-ray diffraction data. It appeared to be isostructural to ammonium thorium phosphate, NH4Th2(PO4)3; in this crystal structure, large channels (5.07 Å~ 3.79 .) located along the c-axis are occupied by NH4+ ions.