Determination of hydration numbers by IR spectrometry

The use of precision IR spectrometry for determining the hydration numbers of species in organic phase was considered. The hydration numbers of HAuCl₄ (n = 3), HFeCl₄ (n = 3), HNO₃ (n = 0), HClO₄ (n = 2), and HCl (n = 1) in 0.64 M (15 vol. %) TBP in CCl₄ were determined.     

Efficient Olefin Epoxidation by Robust Re4 Cluster‐Supported MnIII Complexes with Peracids: Evidence of Simultaneous Operation of Multiple Active Oxidant Species,MnVO,MnIVO,and MnIII?OOC(O)R

Two new tetranuclear chalcocyanide cluster complexes, [{Mn(saloph)H₂O}₄Re₄Q₄(CN)₁₂]?4 CH₃OH? 8 H₂O (saloph=N,N′‐o‐phenylenebis(salicylidenaminato), Q=Se ( 1 ‐Se), Te ( 2 ‐Te)), have been synthesized by the diffusion of a methanolic solution of [PPh₄]₄[Re₄Q₄(CN)₁₂] into a methanolic solution of [Mn(saloph)]⁺. The structure of 2 ‐Te has been determined by X‐ray crystallography. These rhenium cluster‐supported [Mn^III(saloph)] complexes have been found to efficiently catalyze a wide range of olefin epoxidations under mild experimental conditions in the presence of meta‐chloroperbenzoic acid (mCPBA). Olefin epoxidation by these catalysts is proposed to involve the multiple active oxidants Mn^V?O, Mn^IV?O, and Mn^III? OOC(O)R. Evidence in support of this interpretation has been derived from reactivity and Hammett studies, H₂¹⁸O‐exchange experiments, and the use of peroxyphenylacetic acid as a mechanistic probe. Moreover, it has been observed that the participation of Mn^V?O, Mn^IV?O, and Mn^III? OOC(O)R can be controlled by changing the substrate concentration. This mechanism provides the greatest congruity with related oxidation reactions that employ certain Mn complexes as catalysts.     

Reaction of 5-oxo-2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepine with chloral. The synthesis and spatial structure of 5-carbaphosphatrane containing a four-membered ring

Phosphorylation of 2-hydroxyphenyl 2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl ketone with dichloro(phenyl)phosphine gave 5-oxo-2-phenyl-4,4-bis(trifluoromethyl)-4,5-di-hydro-1,3,2-benzodioxaphosphepine. Heating of the latter initiated an intramolecular interaction of the P atom with the carbonyl group. Hydrolysis of the intermediate product yielded 3-hydroxy-2-oxo-2-phenyl-3-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-2,3-di-hydro-1,2λ⁵-benzo[d]oxaphosphole. The reaction was highly stereoselective (P_RC_S/P_SC_R). The reaction of the starting phosphepine with chloral proceeded highly stereoselectively (P_RC_SC_S/P_SC_RC_R) to give a 5-carbaphosphatrane derivative containing a four-membered ring, namely, 1-phenyl-3-trichloromethyl-10,10-bis(trifluoromethyl)-6,7-benzo-2,4,8,9-tetraoxa-1λ⁵-phosphatricyclo[3.3.2.0¹,⁵]decene. The trigonal bipyramid of the 5-carbaphosphatrane derivative is made up of the equatorial O atoms and the apical C atoms.     

Determination of hydration numbers of acids in organic phase by IR spectrometry

By the precision infrared spectrometry the hydration numbers n were determined for a series of acids in 0.64 M tributyl phosphate (CCl₄) and acetonitrile at a concentration of free water 0.01–0.1 M. In tributyl phosphate n = 3.1±0.3 (HAuCl₄); 2.9±0.3 (HFeCl₄); 1.9±0.2 (HClO₄); 1.0±0.2 (HNO₃); 1.0±0.1 (HCl). In acetonitrile n = 3.1±0.7 (HAuCl₄); 1.1±0.4 (HFeCl₄); 2.1±0.2 (HClO₄), 0±0.05 (HNO₃); 0.1±0.15 (HCl).     

A parallel Ugi reaction at students laboratories in the Ural and Moscow

A four-component Ugi reaction was adapted for students education. To this end, a series of almost odorless aromatic isonitriles with donor substituents was reacted with a specific carboxylic acid, phthaloyl glycine, to obtain poorly soluble (although nicely crystallized) products. The process was performed and compared in two versions by using (1) a standard centrifuge for parallel separation of precipitates and (2) parallel filtration with SynCore apparatus. It is shown for a broad series of aliphatic ketones and benzyl amines that the yields are satisfactory and the products require no further purification.     

New scintillators based on barium fluoride crystals and ceramics

Experimental studies on the optical properties of new crystals and ceramics based on CeF₃- and CdF₂-doped barium fluoride were aimed at producing scintillators with a higher light yield level (particularly in the ultra-short wavelength range with a luminescence time of 0.6–0.8 ns) that could be used in the development of fast and low-cost optical sensors for positron emission tomography (PET). Ceramics manufactured on the basis of BaF₂ single crystals with various concentrations of Ce and Cd are transparent in the 300–600 nm wavelength range; this is comparable to BaF₂ single crystals.     

On self-focusing of an ultrashort intense relativistic laser pulse in a plasma

The development of the spatiotemporal (filamentation) instability of a laser pulse upon excitation of a plasma wave is studied numerically and analytically. It is shown that first, as in a medium with inertialless cubic nonlinearity, the filamentation of radiation occurs and then filaments are attracted to each other. The following evolution differs weakly from the evolution of a smoothed wave beam in a medium with inertial nonlinear response.     

An experimental study of pressure fluctuations generated by an open shallow cavity performed using joint time-frequency techniques of data analysis

An experimental study of the flow over a single open shallow cavity is reported. Pressure fluctuations were measured using two cavity models at free-stream Mach numbers 0.3, 0.5, and 0.6. At certain conditions, resonance of acoustic waves inside cavity with disturbances in the shear layer over cavity was observed. Pressure fluctuation characteristics were analysed using Fourier, wavelet, and Hilbert — Huang transforms. Those methods have allowed us to accurately examine the transition of the flow over cavity into resonant state.