Solvation, Ionic and Complex Formation Reactions in Non-Aqeuous Solvents, Volume 6

Preface

1. Introduction

References

2. General Characterization of Solvents

Classification of Non-Aqueous Solvents

Characteristics of Solvent Properties

References

3. Solvent-Solute Interactions

Theoretical Approaches

Solvation, Solvation Number

Solvation with Donor and Acceptor Solvents

References

4. Donor-Acceptor Interactions. The Donor and Acceptor Strengths of Solvents

Empirical Solvent Strength Scales

Characterization of the Donor Strength on the Basis of the Ionization Energy

Characterization of the Donor Strength on the Basis of the Crystal Field Splitting

Characterization of the Donor Strength on the Basis of the Heat of Solvation

Base Strength Towards the Proton

Characterization of the Donor Strength on the Basis of Conductometric Measurements

Characterization of the Donor Strength on the Basis of Polarographic Measurements

Characterization of the Donor Strength by Means of Infrared Spectroscopy

Characterization of the Donor Strength by Means of NMR Spectroscopy

Transition Metal Complex Reference Acceptors in the Investigation of Donor Solvents

The Kamlet-Taft Solvent Basicity Scale

Characterization of the Acceptor Strength on the Basis of the Solvatochrome Effect

Characterization of the Acceptor Strength on the Basis of NMR Measurements

Characterization of the Acceptor Strength on the Basis of Kinetic Measurements

Other Solvent Strength (Polarity) Scales

Intercorrelation of the Various Solvent Strength Scales

Study of Lewis Donor-Acceptor Interactions and Related Problems

Effect of the Parent Solvent

Role of the Experimental Method

Effect of the Reference Acceptor or Reference Donor

The Drago Concept

The Koppel-Palm Concept

The Krygowski-Fawcett Concept

The Gutmann-Mayer Concept

The Linear Solvation Energy Relationship (Kamlet-Taft) Concept

References

5. Experimental Methods Employed in the Study of Non-Aqueous Solutions of Complex Systems

Conductometry

Dielectrometry

Dielectric Relaxation Spectroscopy

UV and Visible Spectroscopy

Circular Dichroism (CD) Spectroscopy

The Solvent Dependence of CD

Infrared and Raman Spectroscopy

Nuclear Magnetic Resonance (NMR) Spectroscopy

Magnetic Susceptibility Examinations

Nuclear Quadrupole Resonance (NQR) Spectroscopy

Electron Paramagnetic Resonance (EPR) Spectroscopy

Mössbauer Spectroscopy in Frozen Solutions

X-ray Diffraction Studies

X-ray Photoelectron Spectroscopy (XPS, ESCA) in Rapidly Frozen Solutions

Positron Annihilation and Positronium Chemistry

Pick-Off Annihilation and the Molecular and Solution Structures

Coordination Chemical Aspects of Positron Annihilation

Ultrasonic Velocity Investigations

Electron Spin Echo Modulation Studies

References

6. Effect of the Solvent on the Structures and Stabilities of Metal Complexes in Solution

Effect of the Donor Strength

Effects of Steric Factors

Effect of Solvation of the Anion

Effect of Solvation of the Outer-Sphere Type

Formation of Auto-Complexes, Mixed Ligand Complexes, DA Molecular Complexes and Polynuclear Complexes

Effect of the Structure of the Solvent

References

7. Effect of the Solvent on the Kinetics and Mechanisms of Coordination Reactions

The Effect of Solvation Strength (Donor or Acceptor Strength) of Solvents

Competitive Preferential Solvation (COPS) Theory

Solvent Dependence of Reactions in Organometallic Chemistry

References

8. Interactions in Solvent Mixtures and their Investigation

Interaction Between the Components of the Solvent Mixture

Solvation Processes in Solvent Mixtures

Complex Formation in Solvent Mixtures

Solvent Dependence of Complex Stability

Equilibrium Studies in Water-Dioxane Solvent Mixtures

Equilibrium Studies in Solvent Mixtures with Varying Compositions

Equilibrium Measurements in Non-Aqueous Solvent Mixtures

Calorimetric Equilibrium Studies

References

9. General Suggestions for the Characterization of Non-Aqueous Solution Systems

Analytical Examination of the Solution

Determination of Moisture Content

Determination of Other Impurities

Purification of Solvents

Removal of the Moisture Content

Molecular Sieves and their Application

Purification Procedures for some Solvents

Characterization of Solvents by their Physical parameters

Characterization of the Solvating Powers of Solvents

Characterization of Solvent Mixtures

References

10. Research Trends in the Future

Subject Index

Solvation, Ionic and Complex Formation Reactions in Non-Aqueous Solvents: Experimental Methods for their Investigation presents the available methods and their particular value in investigating solutions composed of non-aqueous solvents.

This book is composed of 10 chapters and begins with a brief description of the complexity of the interactions possible n solutions. The subsequent chapters deal with a classification of the solvents and empirical solvent strength scales based on various experimental parameters, together with various correlations empirically describing the solvent effect. Other chapters present the methods for the purification of solvents and ways of checking their purity, as well as the individual results achieved during investigations of the solvent effect, particularly the general regularities recognized. The remaining chapters provide a review of the coordination chemistry of non-aqueous solutions.

This book will prove useful to analytical and inorganic chemists.