.

0 (hodnocen0 x )

BK

Budapest : Akadémiai Kiadó, 1983

ISBN 963-05-3097-X

000098451

Rekat.

Preface 11 // 1. Introduction 15 // References 19 // 2. General characterization of solvents 20 // Classification of non-aqueous solvents 20 // Characteristics of solvent properties 23 // References 26 // 3. Solvent-solute interactions 27 // Theoretical approaches 27 // Solvation, solvation number 34 // Solvation with donor and acceptor solvents 38 // References 40 // 4. Donor-acceptor interactions. The donor and acceptor strengths of solvents 42 // Empirical solvent strength scales 42 // Characterization of the donor strength on the basis of the ionization energy 43 // Characterization of the donor strength on the basis of the crystal field splitting 43 // Characterization of the donor strength on the basis of the heat of solvation 45 // Base strength towards the proton 47 // Characterization of the donor strength on the basis of conductometric measurements 48 // Characterization of the donor strength on the basis of polarographic measurements 49 // Characterization of the donor strength by means of infrared spectroscopy 50 // Characterization of the donor strength by means of NMR spectroscopy 51 // Transition metal complex reference acceptors in the investigation of donor solvents 52 // The Kamlet-Taft solvent basicity scale 58 // Characterization of the acceptor strength on the basis of the solvatochrome effect 59 // Characterization of the acceptor strength on the basis of NMR measurements 64 // Characterization of the acceptor strength on the basis of kinetic measurements 66 // Other solvent strength (polarity) scales 67 // Intercorrelation of the various solvent strength scales 69 // Study of Lewis donor-acceptor interactions and related problems 70 // Effect of the parent solvent 70 // Role of the experimental method 74 // Effect of the reference acceptor or reference donor 75 // The Drago concept 76 // The Koppel-Palm concept 79 //

The Krygowski-Fawcett concept 81 // The Gutmann-Mayer concept 83 // The linear solvation energy relationship (Kamlet-Taft) concept 88 // References 90 // 7 // 5. Experimental methods employed in the study of non-aqueous solutions of complex systems 93 // Conductometry 96 // Dielectrometry 99 // Dielectric relaxation spectroscopy 102 // UV and visible spectroscopy 104 // Circular dichroism (CD) spectroscopy 110 // The solvent dependence of CD 111 // Infrared and Raman spectroscopy 114 // Nuclear magnetic resonance (NMR) spectroscopy 127 // Magnetic susceptibility examinations 136 // Nuclear quadrupole resonance (NQR) spectroscopy 138 // Electron paramagnetic resonance (EPR) spectroscopy 139 // Mössbauer spectroscopy in frozen solutions 142 // X-ray diffraction studies 161 // X-ray photoelectron spectroscopy (XPS, ESCA) in rapidly frozen solutions 163 // Positron annihilation and positronium chemistry 167 // Pick-off annihilation and the molecular and solution structures 171 // Coordination chemical aspects of positron annihilation I73 // Ultrasonic velocity investigations 176 // Electron spin echo modulation studies 177 // References 177 // 6. Effect of the solvent on the structures and stabilities of metal complexes in solution 189 // Effect of the donor strength 189 // Effects of steric factors 190 // Effect of solvation of the anion 192 // Effect of solvation of the outer-sphere type 196 // Formation of auto-complexes, mixed ligand complexes, DA molecular complexes and // polynuclear complexes 197 // Effect of the structure of the solvent 199 // References 200 // 7. Effect of the solvent on the kinetics and mechanisms of coordination reactions 203 // The effect of solvation strength (donor or acceptor strength) of solvents 205 // Competitive preferential solvation (COPS) theory 211 // Solvent dependence of reactions in organometallic chemistry 212 //

References 215 // 8 Interactions in solvent mixtures and their investigation 217 // Interaction between the components of the solvent mixture 218 // Solvation processes in solvent mixtures 222 // Complex formation in solvent mixtures 225 // Solvent dependence of complex stability 226 // Equilibrium studies in water-dioxane solvent mixtures 231 // Equilibrium studies in solvent mixtures with varying compositions 234 // Equilibrium measurements in non-aqueous solvent mixtures 237 // Calorimetric equilibrium studies 238 // References 239 // 9. General suggestions for the characterization of non-aqueous solution systems 243 // Analytical examination of the solution 243 // Determination of moisture content 244 // Determination of other impurities 246 // 8 // Purification of solvents 246 // Removal of the moisture content 247 // Molecular sieves and their application  49 // Purification procedures for some solvents 249 // Characterization of solvents by their physical parameters 254 // Characterization of the solvating powers of solvents 256 // Characterization of solvent mixtures 258 // References 259 // 10. Research trends in the future 260 // Subject index 265