Synthetic coordination chemistry : principles and practice /
Synthetic coordination chemistry : principles and practice /
J.A. Davies ... [et al.].
- Singapore ; River Edge, N.J. : World Scientific Pub. Co., c1996.
- 1 online resource (xviii, 452 p.) : ill.
Includes bibliographical references and index.
ch. 1. Synthesis of coordination compounds: theoretical considerations. 1.1. Labile and inert coordination compounds. 1.2. Synthesis of mixed-ligand complexes by co-proportionation. 1.3. The chelate effect. 1.4. The trans-effect. 1.5. The cis-effect. 1.6. Geometric isomerization of square-planar platinum(II) and palladium(II) complexes. 1.7. The effective atomic number concept. 1.8. The 16-/18-electron rule. 1.9. The hard-soft acid-base (HSAB) principle. 1.10. Factors affecting the acid/base properties of coordination compounds. 1.11. Ligand effects on redox potentials of coordination compounds. 1.12. Reactivity of coordinated ligands -- ch. 2. The solubility of coordination compounds: relationship to composition and structure. 2.1. Hydrophilic and lipophilic coordinated ligands. 2.2. Solubility of ionic complexes: counterion effects. 2.3. Changes in solubility through modification of cationic counterions. 2.4. Solubility of complexes in mixed solvents -- ch. 3. Generation of solvento-complexes. 3.1. Halide abstraction reactions. 3.2. Solvento-complexes from redox transformations of coordination compounds. 3.3. Formation of solvento-complexes through reactions of coordinated ligands (non-redox). 3.4. Dehydration reactions of aqua-complexes and formation of solvento-complexes. 3.5. Decarbonylation reactions and removal of other supporting ligands (olefins, acetylenes, arenes, dinitrogen). 3.6. Application of solvento-complexes in the synthesis of bridged hetero- and homopdynuclear complexes. 3.7. Complexes containing coordinated halocarbons -- ch. 4. Homoleptic solvento-complexes: starting materials for preparative coordination chemistry. 4.1. Introduction. 4.2. Synthesis of solvento-complexes by metal oxidation in non-aqueous solvents. 4.3. Synthesis of solvento-complexes by dissolution of salts in non-aqueous solvents. 4.4. Synthesis of solvento-complexes by dehydration of aqua-complexes and hydrated salts. 4.5. Synthesis of solvento-complexes by substitution of ligated solvent molecules. 4.6. Synthesis of solvento-complexes by halide abstraction from salts and complexes -- ch. 5. Synthesis via ion exchange in non-aqueous solvents. 5.1. Ligand substitution by ion exchange in non-aqueous solvents. 5.2. Synthesis of complexes containing classically "noncoordinating" anions as ligands. 5.3. Formation of chelate complexes by ion exchange in non-aqueous solvents. 5.4. Synthesis of complexes containing metal-metal bonds between transition metals. 5.5. Synthesis of complexes containing transition metal-main group metal/metalloid bonds. 5.6. Replacement of counterions in ionic complexes -- ch. 6. Synthesis of bridged complexes and ring-closures. 6.1. Synthesis of bridged complexes. 6.2. Ring-closure reactions -- ch. 7. The electrosynthesis of coordination compounds. 7.1. Electrochemical oxidation and reduction of complexes using inert electrodes. 7.2. Electrochemically induced reactions. 7.3. Electrosynthesis using a sacrificial anode. 7.4. Electrosynthesis at a sacrificial cathode. 7.5. Practical considerations in synthetic electrochemistry -- ch. 8. Non-traditional oxidants in preparative coordination chemistry. 8.1. Nitrosonium, thionitrosonium and nitronium salts. 8.2. Aryldiazonium salts. 8.3. Triphenylcarbenium,tropylium, and other carbenium salts. 8.4. Protic acids. 8.5. Silver, mercury and other metal salts. 8.6. Non-metal halides. 8.7. Aminoxides and other oxygen donors. 8.8. Other selected oxidants. 8.9. "Modification" of water-soluble oxidants. ch. 9. Reductants in preparative coordination chemistry. 9.1. Reduction by metals and amalgams. 9.2. Reduction by organic radical-anions and anions. 9.3. Carbon monoxide and other carbon-containing reductants. 9.4. Sulfur-containing reductants. 9.5. Low oxidation state metal ions. 9.6. Tertiary phosphines and phosphites. 9.7. Other reductants -- ch. 10. Boron and aluminium hydrides in preparative coordination chemistry. 10.1. Applications of boron and aluminum hydrides in the synthesis of metal hydrides. 10.2. Reduction without formation of M-H bonds. 10.3. Application of hydrides as reductants for coordinated carbonyl ligands. 10.4. Reactions of boron and aluminum hydrides with unsaturated hydrocarbyls and related ligands. 10.5. Reactions of boron and aluminum hydrides with other coordinated ligands -- ch. 11. Molecular rearrangements of coordination compounds. 11.1. Rearrangements involving changes in metal-ligand binding sites. 11.2. Rearrangements involving changes in coordination polyhedra. 11.3. Rearrangement of coordinated ligands on a metal framework. 11.4. Rearrangement of [symbol]-olefin complexes to [symbol]-organometallics. 11.5. Rearrangement of acyl ligands to alkyl and carbonyl ligands. 11.6. Interligand oxygen transfer. 11.7. Conversion of phosphite complexes to phosphonate complexes -- ch. 12. Solid state thermal synthesis of coordination compounds. 12.1. The Anderson rearrangement. 12.2. Dehydration and deaquation. 12.3. Syntheses involving abstraction of amine and other neutral ligands. 12.4. Solid state thermal polymerization. 12.5. Syntheses that involve deprotonation of a coordinated ligand followed by ring-closure. 12.6 Thermal deprotonation of coordinated ammine ligands. 12.7. Solid state cyclometallation. 12.8. Thermal decarboxylation and disproportionation. 12.9. Solid state thermal oxidation of tertiary phosphines. 12.10. Solid state geometric isomerization.
Although coordination chemistry naturally centers on the synthesis of coordination compounds, the synthesis of these materials is typically not an end in itself. Coordination compounds are utilized in all branches of chemistry; from theoretical modeling to industrial and consumer products. While a large amount of information is available on coordination chemistry in general and synthetic methods in particular, no comprehensive work has been presented on the preparation of coordination compounds with an emphasis on synthetic strategies rather than on detailed descriptions of specific syntheses. The goal of this book is to provide an approach to coordination chemistry that is based upon preparative strategies. The main aim of the authors is to present a systematic classification of synthetic reactions rather than an encyclopedic listing of experimental results. Hence, the coverage is more selective than exhaustive. Despite this, the book provides access to the original literature with ca. 2000 references. The edition is well-illustrated and contains almost 250 schemes, figures and illustrations of crystal structures of selected complexes.
Electronic reproduction.
Singapore :
World Scientific Publishing Co.,
1996.
System requirements: Adobe Acrobat Reader.
Mode of access: World Wide Web.
9789812831378
Coordination compounds--Synthesis.
Electronic books.
QD474 / .S96 1996
541.2/242
Includes bibliographical references and index.
ch. 1. Synthesis of coordination compounds: theoretical considerations. 1.1. Labile and inert coordination compounds. 1.2. Synthesis of mixed-ligand complexes by co-proportionation. 1.3. The chelate effect. 1.4. The trans-effect. 1.5. The cis-effect. 1.6. Geometric isomerization of square-planar platinum(II) and palladium(II) complexes. 1.7. The effective atomic number concept. 1.8. The 16-/18-electron rule. 1.9. The hard-soft acid-base (HSAB) principle. 1.10. Factors affecting the acid/base properties of coordination compounds. 1.11. Ligand effects on redox potentials of coordination compounds. 1.12. Reactivity of coordinated ligands -- ch. 2. The solubility of coordination compounds: relationship to composition and structure. 2.1. Hydrophilic and lipophilic coordinated ligands. 2.2. Solubility of ionic complexes: counterion effects. 2.3. Changes in solubility through modification of cationic counterions. 2.4. Solubility of complexes in mixed solvents -- ch. 3. Generation of solvento-complexes. 3.1. Halide abstraction reactions. 3.2. Solvento-complexes from redox transformations of coordination compounds. 3.3. Formation of solvento-complexes through reactions of coordinated ligands (non-redox). 3.4. Dehydration reactions of aqua-complexes and formation of solvento-complexes. 3.5. Decarbonylation reactions and removal of other supporting ligands (olefins, acetylenes, arenes, dinitrogen). 3.6. Application of solvento-complexes in the synthesis of bridged hetero- and homopdynuclear complexes. 3.7. Complexes containing coordinated halocarbons -- ch. 4. Homoleptic solvento-complexes: starting materials for preparative coordination chemistry. 4.1. Introduction. 4.2. Synthesis of solvento-complexes by metal oxidation in non-aqueous solvents. 4.3. Synthesis of solvento-complexes by dissolution of salts in non-aqueous solvents. 4.4. Synthesis of solvento-complexes by dehydration of aqua-complexes and hydrated salts. 4.5. Synthesis of solvento-complexes by substitution of ligated solvent molecules. 4.6. Synthesis of solvento-complexes by halide abstraction from salts and complexes -- ch. 5. Synthesis via ion exchange in non-aqueous solvents. 5.1. Ligand substitution by ion exchange in non-aqueous solvents. 5.2. Synthesis of complexes containing classically "noncoordinating" anions as ligands. 5.3. Formation of chelate complexes by ion exchange in non-aqueous solvents. 5.4. Synthesis of complexes containing metal-metal bonds between transition metals. 5.5. Synthesis of complexes containing transition metal-main group metal/metalloid bonds. 5.6. Replacement of counterions in ionic complexes -- ch. 6. Synthesis of bridged complexes and ring-closures. 6.1. Synthesis of bridged complexes. 6.2. Ring-closure reactions -- ch. 7. The electrosynthesis of coordination compounds. 7.1. Electrochemical oxidation and reduction of complexes using inert electrodes. 7.2. Electrochemically induced reactions. 7.3. Electrosynthesis using a sacrificial anode. 7.4. Electrosynthesis at a sacrificial cathode. 7.5. Practical considerations in synthetic electrochemistry -- ch. 8. Non-traditional oxidants in preparative coordination chemistry. 8.1. Nitrosonium, thionitrosonium and nitronium salts. 8.2. Aryldiazonium salts. 8.3. Triphenylcarbenium,tropylium, and other carbenium salts. 8.4. Protic acids. 8.5. Silver, mercury and other metal salts. 8.6. Non-metal halides. 8.7. Aminoxides and other oxygen donors. 8.8. Other selected oxidants. 8.9. "Modification" of water-soluble oxidants. ch. 9. Reductants in preparative coordination chemistry. 9.1. Reduction by metals and amalgams. 9.2. Reduction by organic radical-anions and anions. 9.3. Carbon monoxide and other carbon-containing reductants. 9.4. Sulfur-containing reductants. 9.5. Low oxidation state metal ions. 9.6. Tertiary phosphines and phosphites. 9.7. Other reductants -- ch. 10. Boron and aluminium hydrides in preparative coordination chemistry. 10.1. Applications of boron and aluminum hydrides in the synthesis of metal hydrides. 10.2. Reduction without formation of M-H bonds. 10.3. Application of hydrides as reductants for coordinated carbonyl ligands. 10.4. Reactions of boron and aluminum hydrides with unsaturated hydrocarbyls and related ligands. 10.5. Reactions of boron and aluminum hydrides with other coordinated ligands -- ch. 11. Molecular rearrangements of coordination compounds. 11.1. Rearrangements involving changes in metal-ligand binding sites. 11.2. Rearrangements involving changes in coordination polyhedra. 11.3. Rearrangement of coordinated ligands on a metal framework. 11.4. Rearrangement of [symbol]-olefin complexes to [symbol]-organometallics. 11.5. Rearrangement of acyl ligands to alkyl and carbonyl ligands. 11.6. Interligand oxygen transfer. 11.7. Conversion of phosphite complexes to phosphonate complexes -- ch. 12. Solid state thermal synthesis of coordination compounds. 12.1. The Anderson rearrangement. 12.2. Dehydration and deaquation. 12.3. Syntheses involving abstraction of amine and other neutral ligands. 12.4. Solid state thermal polymerization. 12.5. Syntheses that involve deprotonation of a coordinated ligand followed by ring-closure. 12.6 Thermal deprotonation of coordinated ammine ligands. 12.7. Solid state cyclometallation. 12.8. Thermal decarboxylation and disproportionation. 12.9. Solid state thermal oxidation of tertiary phosphines. 12.10. Solid state geometric isomerization.
Although coordination chemistry naturally centers on the synthesis of coordination compounds, the synthesis of these materials is typically not an end in itself. Coordination compounds are utilized in all branches of chemistry; from theoretical modeling to industrial and consumer products. While a large amount of information is available on coordination chemistry in general and synthetic methods in particular, no comprehensive work has been presented on the preparation of coordination compounds with an emphasis on synthetic strategies rather than on detailed descriptions of specific syntheses. The goal of this book is to provide an approach to coordination chemistry that is based upon preparative strategies. The main aim of the authors is to present a systematic classification of synthetic reactions rather than an encyclopedic listing of experimental results. Hence, the coverage is more selective than exhaustive. Despite this, the book provides access to the original literature with ca. 2000 references. The edition is well-illustrated and contains almost 250 schemes, figures and illustrations of crystal structures of selected complexes.
Electronic reproduction.
Singapore :
World Scientific Publishing Co.,
1996.
System requirements: Adobe Acrobat Reader.
Mode of access: World Wide Web.
9789812831378
Coordination compounds--Synthesis.
Electronic books.
QD474 / .S96 1996
541.2/242