In memoriam Ludwig F. Audrieth

Transcription

1 In memoriam Ludwig F. Audrieth

2 Coordination Chemistry in Non-Aqueous Solutions V. Gutmann 1968 Springer-Verlag Wien,0 N ew York

3 Dipl.-Ing. Dr. techno (Vienna), Ph. D. (Cantab.), Sc. D. (Cantab.) VIKTOR GUTMANN Professor of Inorganic Chemistry, Technische Hochschule Wien, Austria With 10 Figures ISBN-13: DOl: / e-isbn-13: All rights reserved No part of this book may be translated or reproduced in any form without written permission from Springer-Verlag 1968 by Springer-VerlagfWien Softcover reprint of the hardcover 1st edition 1968 Library of Congress Catalog Card Number Title No. 9226

4 Preface Considerable attention has been focussed on non-aqueous chemistry in the last decade and this situation has arisen no doubt from a realization of the vast application of this branch of chemistry. Within this field much energetic work has been channelled into the determination of the coordination chemistry of transition metals in these solvent 8ystems. Elaborate experimental techniques have been developed to discover, in particular, the magnetic and spectral properties of complex compounds, and the theoretical background of such systems has been expanded to corroborate, as far as possible, the experimental results. This text has, however, a different bias from many books currently available on this branch of chemistry, and is designed to be a survey of known facts on many of the non-aqueous solvents currently in use mainly in the field of halogen chemistry, together with a discussion of these facts in the light of accepted principles. As such, it is hoped to close a gap in the literature of which many workers and advanced students in this field will be aware. The treatment is meant to be selective rather than completely comprehensive and must unevitably reflect some of the special interests of the author. The solvents are classified from the point of view of coordination chemistry, as either "acceptors" or "donors" and reactions occurring in the solutions are related to the coordinating properties of the solvents. For this reason, the various physicochemical methods in use in the authors own laboratories, and the semiquantitative data thereby available, have been utilized to establish the coordination forms of transition metals in various non-aqueous solutions and to correlate the results with the various solvent properties. The reader will, however, not find in the text discussion of ligand field theory, analytical applications of somc of the reactions mentioned, or the electrochemistry (including polarography) of the solution8, because these aspects of non-aqueous chemistry, although of extense interest, are outside the scope of this volume. It has been attempted, however, to present apart from the treatment of principles of coordination chemistry in non-aqueous solvents, a description of a large variety of solvents and of many reactions occurring in their solutions. More than 850 references have been included. It is hoped, in this way to approach bot.h the advanced student and, in fact, every chemist interested in solution chemistry. I wish to thank all those who have encouraged me in writing this book, in particular to the late Professor LUDWIG F. AUDRIETH, to whom this book is dedicated and to Professor HARRY H. SISLER, University of Florida, Gainesville/Fla. I wish also to thank Dr. J. FROST for his valuable assistance in preparing this text in English and Dipl.-Ing. M. BERMANN for proof reading and indexing. Vienna, Fall 1967 V. GU'l'MANN

5 Contents Chapter I General 1. Introduction Classification of Solvents 3. Physical Properties Acids and Bases (Acidic and Basic Function) A. Classical Definition B. The Protonic Concept... C. The Solvent-System Concept D. The lonotropic Definitions. E. The Lewis Concept F. Hard and Soft Acids and Bases 5. Techniques with Non-Aqueous Solvents Chapter II Principles of Coordination Chemistry in Non-Aqueous Solutions 1. Donor Solvents and Acceptor Solvents 2. Coordinating Properties of Solvents. A. Donor Strength B. The Donor Number.... C. Prediction of Donor-Acceptor Interactions D. Hydrogen Bonding E. Steric Factors F. Solubilities Coordination Equilibria in Solution. A. Formation of a (Non-solvated) Complex Anion B. Ionization and Dissociation of a Solvate Complex C. Autocomplex Formation.. 4. Solvation and Donor Properties Chapter III Coordination Chemistry in Proton-containing Donor Solvents 1. General Properties of Proton-containing Solvents. 2. Liquid Ammonia. 3. Hydrazine Hydrogen Sulphide Formamide and Acetamide 6. Formic Acid and Acetic Acid 7. Alcohols.... Chapter IV Proton-containing Acceptor Solvents 1. Introduction Hydrogen Fluoride Page

6 VIII Contents 3. Liquid Hydrogen Chloride, Hydrogen Bromide and Hydrogen Iodide Liquid Hydrogen Cyanide Sulphuric Acid Nitric Acid and Phosphoric Acid Fluorospulphuric Acid, Chlorosulphuric Acid, Difluorophosphoric Acid and Disulphuric Acid Chapter V Proton free Acceptor Solvents 1. Covalent Oxides..... A. Liquid Sulphur Dioxide B. Liquid Dinitrogen Tetroxide 2. Covalent Fluorides A. Bromine(III) fluoride and Chlorine(III) fluoride B. Iodine(V) fluoride. C. Arsenic(III) fluoride 3. Covalent Chlorides 4. Covalent Bromides 5. Molten Iodine Chapter VI Oxyhalide Solvents 1. Oxyhalides with Low Donor Numbers 2. Oxyhalides with Medium Donor Numbers Chapter VII Certain Donor Solvents 1. 1,2-Dichloroethane (DNsbCI6 = 0.1) Nitromethane (NM) (DNsbCI6 =2.7) and Nitrobenzene (NB) (DNsbCI5 =4.4) Acetic Anhydride (AA) (DNsbCI5 = 10.5) Acetonitrile (AN) (DNsbCl6 = 14.1) Sulpholane (Tetramethylenesulphone) (DNsbCI6 = 14.8) Propanediol-l,2-carbonate (PDC) (DNsbCI6 = 15.1) Acetone (DNsbCI6 = 17.0) Ethyl Acetate (DNsbCl6 = 17.1) Diethylether (DNsbCI5 = 19.2) Trimethyl Phosphate (TMP) (DNsbCI6 = 23) Tributyl Phosphate (TBP) (DNsbCl5 = 23.7) Dimethylformamide (DMF) (DNsbCl5 ~ 2 7. ) N,N-Dimethylacetamide (DMA) (DNsbCI6 =27.8) Dimethyl Sulphoxide (DMSO) (DNsbCI5 = 29.8) Hexamethylphosphoramide (HMPA) (DNsbCI5 = 38.8) 159 Chapter VIII Coordination Chemistry of Certain Transition Metal Ions in Donor Solvents 1. Iodide Ions as Competitive Ligands.. 2. Bromide Ions as Competitive Ligands. 3. Chloride Ions as Competitive Ligands. 4. Azide Ions as Competitive Ligands.. 5. Thiocyanate Ions as Competitive Ligands 6. Cyanide Ions as Competitive Ligands.. 7. An Attempt to AssigIl a Donor Number to Anions 8. Conclusion Index