Ruthenium bis(phosphinite) pincer complexes

Resorcinol-based ruthenium bis(phosphinite) complexes were synthesized. Complexes RuCl(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (9) and RuH(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (10) were obtained by cyclometallation of 1,3-(Bu^t ₂PO)₂C₆H₃ with RuCl₂(DMSO)₄ in 2-methoxyethanol in the presence of Hünig’s base. The interconversion of complexes 9 and 10 was studied. The addition of carbon monoxide to complexes 9 and 10 yielded 18e adducts, RuCl(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (11) and RuH(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (12), respectively. In the case of complex 9, this reaction is reversible. Reaction of complex 10 with trifluoroacetic acid resulted in complex Ru(CF₃COO)(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (13), which reacted with carbon monoxide to give complex Ru(CF₃COO)(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (14). Based on the IR spectral data, the TFA ligand in complexes 13 and 14 is bound in a bi- and monodentate fashion, respectively. The structure of compound 9 was determined by X-ray diffraction analysis.     

Azines and azoles: CXXIX. Synthesis,structure, and some reactions of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-ones

Reactions of 2-aryl-4-chloro-6H-1,3-thiazin-6-ones with sodium sulfide in aqueous alcohol at 18–20°C led to the formation of a readily separable mixture of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-one sodium salts (yield >70%) and bis(2-aryl-6-oxo-6H-1,3-thiazin-4-yl) sulfides (<10%). The latter can also be obtained in more than 50% yield by treatment of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-one sodium salts with 2-aryl-4-chloro-6H-1,3-thiazin-6-ones. Methylation of 2-aryl-4-sulfanyl-6H-1,3-thiazin-6-ones afforded the corresponding methylsulfanyl derivatives (yield >90%) regardless of the alkylating agent, solvent, temperature, reactant concentration, and their ratio. 2-Aryl-4-sulfanyl-6H-1,3-thiazin-6-ones in the crystalline state and in solutions in polar and nonpolar protic and aprotic solvents exist preferentially as 4-sulfanyl-6-oxo tautomers, and they undergo almost complete ionization in neutral aqueous, alcoholic, and aqueous-alcoholic media (pK _a = 4.3). Reactions of 4-sulfanyl-2-phenyl-6H-1,3-thiazin-6-one with ammonia, amines, and difunctional N-centered nucleophiles involve cleavage of the C⁶-S bond in the thiazine ring and subsequent recyclization of linear intermediates to pyrimidines and diazole derivatives. The structure of the isolated compounds was confiirmed by ¹H and ¹³C NMR, IR, and UV spectra.     

Isoprenoid-chained lipid β-XylOC16+4—A novel molecule for in meso membrane protein crystallization

Here we report a successful use of a recently developed isoprenoid-chained lipid family for in meso crystallization of membrane proteins. The isoprenoid-chained lipid 1-O-(3,7,11,15-tetramethylhexadecyl)-β–d-xyloside (β-XylOC₁₆₊₄) used as a host lipid for in meso crystallization provided high quality bacteriorhodopsin (bR) crystals (P6₃ space group) diffracting to high resolution and characterized by low twinning ratio. β-XylOC₁₆₊₄ has an isoprenoid chain with methyl branches at each 4th position and a xylose group in the water-soluble part. These peculiarities make the lipid clearly distinguishable in the bR crystalline lattice and provides a unique opportunity to study the role of the host lipid in the in meso crystallization. We conclude that β-XylOC₁₆₊₄ may have a general application for in meso crystallization for a wide range of membrane proteins. The cubic phase of β-XylOC₁₆₊₄ is present over a wide range of temperatures and is stable at low temperature (down to about 8 °C). This opens up the possibility of using temperature as a tool for the optimization of in meso crystallization with additional advantages for the crystallization of membrane proteins at lower temperatures where the proteins of interest may be more stable.     

Alpha-decay fine structures of U isotopes and systematics for isotopic chains of Po and Rn

A model of the cluster radioactivity of even-even nuclei is presented. In this model, the zero-point vibrations in the charge-asymmetry coordinate determine the cluster formation (spectroscopic factor), while the tunneling in the coordinate of the relative separation of the centers of mass of the cluster and the daughter nucleus determines the penetrability of the barrier of the nucleus-nucleus potential. The quality of the model is demonstrated for describing cluster decay half-lives and the fine structure in alpha decays of even-even U isotopes. The model is applied to describe the alpha decays in the isotopic chains of Po, Rn, and U. The correspondence of the calculated half-lives to the Geiger-Nuttall law is discussed.     

Synthesis and structures of palladium P,C,P pincer complexes based on ferrocene

Russian Chemical Bulletin -     

The aggregation of branched polyethylenimine and cationic surfactants in aqueous systems

The aggregation of binary mixtures of branched polyethylenimine with a molecular mass of 30 000 and cationic surfactants, such as cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, or cetyldimethyl(2-hydroxyethyl)ammonium bromide, in aqueous solutions is studied. The critical micellization concentrations, as well as the sizes and shapes of aggregates, are determined by conductometry, small-angle neutron scattering, and dynamic light scattering methods. Catalytic activity of cationic surfactant-polyethylenimine compositions in the hydrolysis of tetracoordinated phosphorus acid 4-nitrophenyl esters is studied via spectrophotometry. The influence of spatial characteristics of aggregates on the catalytic activity and selectivity of nanostructured polymeric systems is revealed.     

Stability thresholds of surface phases during electroadsorption of organic compounds from electrolyte solutions

Properties of the interface between a mercury electrode and an electrolytic solution containing surface-active substances are explored. A generalized formulation of conditions for thermodynamic equilibrium during electroadsorption (equation of state) is given with use made of the principle of a minimum free energy of the interface at a zero entropy production (de Donder-Prigogine-Defay). The states on which the second differential of the surface tension is degenerate belong to the stability threshold (lines of inflection points).