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Coordination Chemistry in Non-Aqueous Solutions, Softcover reprint of the original 1st ed. 1968

Langue : Anglais

Auteur :

Couverture de l’ouvrage Coordination Chemistry in Non-Aqueous Solutions
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 tran­ sition 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.
I General.- 1. Introduction.- 2. Classification of Solvents.- 3. Physical Properties.- 4. Acids and Bases (Acidic and Basic Function).- A. Classical Definition.- B. The Protonic Concept.- C. The Solvent-System Concept.- D. The Ionotropic Definitions.- E. The Lewis Concept.- F. Hard and Soft Acids and Bases.- 5. Techniques with Non-Aqueous Solvents.- 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.- 3. 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.- III Coordination Chemistry in Proton-containing Donor Solvents.- 1. General Properties of Proton-containing Solvents.- 2. Liquid Ammonia.- 3. Hydrazine.- 4. Hydrogen Sulphide.- 5. Formamide and Acetamide.- 6. Formic Acid and Acetic Acid.- 7. Alcohols.- IV Proton-containing Acceptor Solvents.- 1. Introduction.- 2. Hydrogen Fluoride.- 3. Liquid Hydrogen Chloride, Hydrogen Bromide and Hydrogen Iodide.- 4. Liquid Hydrogen Cyanide.- 5. Sulphuric Acid.- 6. Nitric Acid and Phosphoric Acid.- 7. Fluorospulphuric Acid, Chlorosulphuric Acid, Difluorophosphoric Acid and Disulphuric Acid.- 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.- VI Oxyhalide Solvents.- 1. Oxyhalides with Low Donor Numbers.- 2. Oxyhalides with Medium Donor Numbers.- VII Certain Donor Solvents.- 1. 1,2-Dichloroethane (DNSbCl5 = 0.1).- 2. Nitromethane (NM) (DNSbCl5) and Nitrobenzene (NB) (DNSbCl5 = 4.4).- 3. Acetic Anhydride (AA) (DNSbCl5 = 10.5).- 4. Acetonitrile (AN) (DNSbci6 = 14.1).- 5. Sulpholane (Tetramethylenesulphone) (DNSbCl5 = 14.8).- 6. Propanediol-1,2-carbonate (PDC) (DNSbCl5 = 15.1).- 7. Acetone (DNSbCl5 = 17.0).- 8. Ethyl Acetate (DNSbCl5 = 17.1).- 9. Diethylether (DNSbCl5 = 19.2).- 10. Trimethyl Phosphate (TMP) (DNSbCl5 =23).- 11. Tributyl Phosphate (TBP) (DNSbCl5 = 23.7).- 12. Dimethylformamide (DMF) (DNSbCl5~27).- 13. N,N-Dimethylacetamide (DMA) (DNSbCl5 = 27.8).- 14. Dimethyl Sulphoxide (DMSO) (DNSbCl5 = 29.8).- 15. Hexamethylphosphoramide (HMPA) (DNSbCl5 = 38.8).- 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 Assign a Donor Number to Anions.- 8. Conclusion.

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