Synthesis and base hydrolysis kinetics of the nitrile complexes [Co(tetren)NCR]3+ (R=Me,Ph and p-MeOC6 H4) and the synthesis and kinetics of formation of the tetrazolato complexes [Co(tetren)N4R]2+ (R=Me and Ph; tetren=1,11-diamino-3,6,9-triazaundecane) by reaction with azide ion

The N-bonded nitrile complexes -[Co(tetren)NCR]³⁺ (R=Me, Ph, p-MeOC₆ H₄) have been prepared by the reaction of -[Co(tetren)OH₂]³⁺ with the corresponding nitrile. The kinetics of base hydrolysis have been studied by pH-stat methods. The reactions involve an SN₁CB displacement of the nitrile to give the hydroxopentamine; nucleophilic attack at the nitrile carbon to give the corresponding carboxamido complex does not occur. NaN₃ reacts with the nitrile complexes in slightly acidic solution (pH ca. 5.7) to give the tetrazolato complexes [Co(tetren)N₄ R]²⁺ (R=Me, Ph) which have been characterised. The reaction of azide ion with -[Co(tetren)NCMe]³⁺ has been studied kinetically. The reaction is biphasic involving the initial rapid formation of the N₁-bonded (5-methyltetrazolato) pentaminecobalt(III) complex with k=2×10^–2dm³ mol^–1s^–1 at 25°C followed by the slow isomerisation to the N₂-bonded complex with k=3.5×10^–5s^–1 at pH 5.7.     

The preparation of copper(II) and copper(I) salts in acetonitrile using group VA and VB pentafluorides

Copper(II) fluorine reacts with the pentafluorides, TaF₅, PF₅, and AsF₅, in acetonitrile to give solvated Cu^II, hexafluoroanion salts. These react with copper metal to give the corresponding Cu^I compounds. Similar reactions occur between AsF₅ and silver(I) or thallium(I) fluorides, but silver(II) fluoride reacts with MeCN, and Ag^I hexafluoroarsenate is formed. PF₅ oxidises Cu slowly in MeCN to give Cu^I hexafluorophosphate, but AsF₅ has no oxidising ability towards metals in MeCN. Spectroscopic data for Cu(MF₆)₂·5MeCN and Cu(MF₆)·4MeCN (M = Ta or P) are discussed.     

Evaluation of NMR spectroscopy for the quantitative characterization of urea-formaldehyde resins

A comparative evaluation has been made of both proton and (13)C nuclear magnetic resonance techniques in the quantitative characterization of commercial urea-formaldehyde resins. There is good agreement between data derived from (13)C NMR spectra and from (1)H high-field continuous wave, or low-field (Fourier transform) NMR spectra. Low-field continuous wave proton spectra exhibit inferior resolution and provide inaccurate quantitative data. Combination of (13)C and proton NMR with nitrogen analysis gives a quantitative characterization technique for these resins.     

Characterisation of cross-linked poly(acryloylmorpholines) as matrices for aqueous gel permeation chromatography

The characterisation of two cross-linked poly(acryloylmorpholines), Enzacry Gel K1 and Enzacryl Gel K2, as matrices for aqueous gel permeation chromatography is described. Near ideal plots of logarithm molecular weight versus distribution coefficient, K_d, are obtained for polyethylene glycols and linear, oligomeric α,ω-diols approximate molecular weight ( _n) fractionation ranges being 0–4000 and 0–20,000 for Enzacryl Gel K1 and Enzacryl Gel K2, respectively. Anomalous retardation of the Schardinger dextrins, cyclomaltohexose and cyclomaltoheptose, is observed although linear maltosaccharides behave normally. The internal gel volumes, calculated from column elution data in water, are significantly larger than the volumes of solvent imbibed by the dry column packings on constituting the gel. Internal gel volumes and solvent imbibition volumes in water are compared with the corresponding values obtained in chloroform and tetrahydrofuran. The two parameters are discussed, in the case of Enzacryl Gel K2 in water and chloroform, in the light of plots of logarithm viscometric hydrodynamic volume versus K_d for polyethylene glycols.     

The Effect of Relationship Characteristics and Relational Communication on Experiences of Hurt From Romantic Partners

This study expands the relational turbulence model (RTM; Solomon & Knobloch,) by theorizing about how characteristics of relationships and relational judgments influence people's experiences of hurtful messages. Previous applications of RTM to hurt have uncovered associations among relational characteristics that influence people's hurtful experiences; however, the process by which these characteristics influence experiences of hurt remains unclear. We propose that relational communication (specifically, perceptions of dominance, and disaffiliation) is the mechanism linking relational qualities to hurt. A multigroup SEM was conducted to test for the possibility of sex differences. Results showed that people's experiences of hurt vary as a function of both relationship characteristics and relational inferences. Results also indicated a difference in path coefficients for males and females.