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This, the second and final volume of Reactions of Coordinated Ligands, describes the chemistry of ligands bound through non-carbon atoms, and of coordinated carbon dioxide. As before, emphasis is on the underlying mechanisms, which provide a unity of understanding for superficially disparate processes. The wide range of topics covered illustrates well both the versatility and the usefulness of coordination chemistry in the controlled activation of ligands. Looking to the future, carbon dioxide is the feedstock of last resort. The homogeneous reduction of dinitrogen to ammonia now seems unlikely to replace the Haber process, but solution reactions also lead to more complex, varied, and valuable products. Nitrogen monoxide, a "non innocent" ligand, impinges as pollutant and reagent. Its rich chemistry stems from its linked roles as three-electron donor, and as extremely powerful -acceptor. In the hydrolysis and condensation of complexed amides, esters etc. , metals act both as templates and as tunable and poly functional Lewis acids. Here the control of hydrophobic and steric interactions begins to model the subtle mechanisms of biological specificity. Finally, phosphorus and sulfur are imporant both as ligand atoms in themselves, and as anchors for other functionalities. I would like to thank all those who have been involved in the writing and production of this work, and also my colleagues old and new, at Glasgow and the University of North Texas, for their support. Paul S. Braterman v CONTENTS 1. Reactions of Coordinated Carbon Dioxide 1 J. D. Miller 1.
Sommario
1. Reactions of Coordinated Carbon Dioxide.- 1. Introduction.- 2. The Properties of Carbon Dioxide.- 3. Complexes containing CO2 as a Ligand.- 4. Subsequent reactions of Complexes Containing CO2.- References.- 2. Reactions of Coordinated Dinitrogen and Related Species.- 1. Introduction.- 2. Methods for Preparing Dinitrogen Complexes.- 3. Bonding Modes and Charge Distribution of Ligating Dinitrogen.- 4. Reactions of Ligating Dinitrogen.- 5. More Recent Results.- 6. Conclusion.- References.- 3. Reactions of Nitrosyls.- 1. Introduction.- 2. The Nitroprusside Ion, [Fe(CN)5(NO)]2?, and Related Pentacyanonitrosyls.- 3. Reduction of Nitrosyls.- 4. Reactions of Nitrosyls with Nucleophiles.- 5. Reactions of Nitrosyls with Electrophiles.- 6. Formation of Carbon-Nitrogen Bonds.- 7. Coupling, Dimerization and Disproportionation of Nitrogen Monoxide in Nitrosyl Complexes.- 8. Exchange, Substitution, and Transfer of the Nitrosyl Ligand.- 9. Miscellaneous Reactions of Nitrosyls.- References.- 4. Hydrolysis and Condensation Reactions of O- and N-bound Ligands.- 1. Introduction.- 2. Hydrolysis of Amino Acid Esters and Amides, Peptides.- 3. Condensation Reactions of Amino-Acids Coordinated to Metal Ions.- 4. Hydrolysis of Carboxylic Esters and Amides.- 5. Hydrolysis of Nitriles.- 6. Hydrolysis of Phosphate Esters.- 7. Hydrolysis of Sulfate Esters.- 8. Hydrolysis of Epoxides.- 9. Hydrolysis of Glycosides and Acetals.- 10. Hydrolysis of Anhydrides.- 11. Acyl Transfer Reactions.- 12. Imines.- 13. Polymer-Metal Complexes.- 14. More Recent Developments.- References.- 5. Reactions of Coordinated Phosphorus and Sulfur Ligands.- 1. Reactions of Phosphorus and Related Ligands.- 2. Reactions of Sulfur Ligands.- References.- Abbreviations.
