Journal of Inorganic and Nuclear Chemistry最新文献

Mössbauer spectrsocopy has been used to study six 1:1 triphenyltin chloride, four 1:2 dimethyltin dichloride and one 1:1 trimethyltin chloride sulfoxide complexes.

An increase in quadrupole splitting on complexation was found for all complexes, although it remains practically constant for each acceptor molecule. While the isomer shifts of the triphenyltin complexes are constant and, furthermore, are approximately the same as that for neat triphenyltin chloride, a significant decrease was observed on complexation of dimethyltin dichloride and trimethyltin chloride.

From the temperature dependence of the area under the Mössbauer lines it was possible to estimate the Debye temperatures for the dimethylsulfoxide-triphenyltin chloride and the di-n-propylsulfoxide-dimethyltin dichloride complexes.

Measurements of CO pressure over the thorium dioxide, thorium dicarbide, carbon phase region were made in the range 1328–1976 K. These values were used with other consistent measurements to derive the 298 K second-law heat of formation and entropy 129±6 kJ/mol and 67.0±3 J·mol⁻¹·K⁻¹, and the third-law heat of formation −122±9 kJ/mol, for thorium dicarbide.

The complexes W(CO)₂(PPh₃)(q)₂, W(CO)₂(PPh₃)(pic)₂ and W(CO)₂(PPh₃)(dsp) (where Ph = C₆H₅, q⁻ = 8-quinolinolato, pic⁻ = picolinato, and dsp²⁻ = the anion of the Schiff-base N,N′-disalicylidene-1,2-phenylene-diamine) have been synthesized. The physical properties of these complexes are indicative of seven-coordinate mixed-ligand tungsten(II) chelates. W(CO)₂(PPh₃)(pic)₂ is the most photochemically reactive and W(CO)₂(PPh₃)(q)₂ is the most thermally reactive. Evidence that the steric effects of the quadriadentate dsp²⁻ ligand cause a change in the overall seven-coordinate sterochemistry is presented.

The solvent extraction equilibrium of boron extraction has been studied for petroleum ether solutions of 2-ethyl-1,3-hexanediol (EHD) and 2-chloro-4-(1,1,3,3-tetramethylbutyl)-6-methylol-phenol (CTMP), employed both singly and in admixture. Theoretical considerations are developed to account semi-quantitatively for observed trends in extraction with changes in pH and organic reagent concentration. The mixed reagents in a 1 : 1 concentration ratio give a much enhanced extraction in the pH range 8–12 and extraction becomes essentially pH independent when the EHD/CTMP ratio is 3 : 1. Boron extraction is largely unaffected by changes in the type of cation present (Na⁺, Ca²⁺ or Mg²⁺). These observations are interpreted in terms of the opposing pH dependences of the two reagents and of the formation of different mixed complexes in the organic phase. The possible application of mixed-reagent solvent extraction is discussed in terms of boron pollution control.

A new approximate formulation describing the electrostatic contribution to the excess free energy of electrolyte solutions is presented. The final equation contains only one parameter and reduces to the Debye-Huckel limiting law at low enough concentrations. It represents the experimental data nicely for the series of alkali metal halides out to quite high concentration, and clarifies certain difficulties in interpretation of solvent isotope effect data with extended theories now in widespread use.

The title compound crystallizes in the triclinic system, space group $\text{P}\text{1}$ with a = 11.512(3), b = 9.387(3), c = 6.757(2) Å, α = 105.6(4), β = 96.8(4) and γ = 107.0(4)° and Z = 2. The structure is built up from two distinct coordination polyhedra, one is formed by the uranium which is at a centre of a pentagonal bipyramid, the other by the potassium cations heptacoordinate to oxygen atoms either belonging to the maleic ligands or to the uranyl group. The uranium polyhedra are connected through bridging maleato groups. The maleato-U-maleato chains in the direction of the c axis are held together through the potassium coordination polyhedra.