Preface.- Acknowledgements.- 1: Introduction.- 1.1. Catalysis. 1.2. Homogeneous catalysis. 1.3. Historical notes on homogeneous catalysis. 1.4. Characterization of the catalyst. 1.5. Ligand effects. 1.6. Ligands according to donor atoms. 2: Elementary Steps.- 2.1. Creation of a 'vacant' site and co-ordination of the substrate. 2.2. Insertion versus migration. 2.3. beta-Elimination and de-insertion. 2.4. Oxidative addition. 2.5. Reductive elimination. 2.6. alpha-Elimination reactions. 2.7. Cycloaddition reactions involving a metal. 2.8. Activation of a substrate toward nucleophilic attack. 2.9. sigma-Bond metathesis. 2.10. Dihydrogen activation. 2.11. Activation by Lewis acids. 2.12. Carbon-to-phosphorus bond breaking. 2.13. Carbon-to-sulfur bond breaking. 2.14. Radical reactions. 3: Kinetics.- 3.1. Introduction. 3.2. Two-step reaction scheme. 3.3. Simplifications of the rate equation and the rete-determining step. 3.4. Determining the selectivity. 3.5. Collection of rate data. 3.6. Irregularities in catalysis. 4: Hydrogenation.- 4.1. Wilkinson's catalyst. 4.2. Asymmetric hydrogenation. 4.3. Overview of chiral bidentate ligands. 4.4. Monodentate ligands. 4.5. Non-linear effects. 4.6. Hydrogen transfer. 5: Isomerisation.- 5.1. Hydrogen shifts. 5.2. Asymmetric isomerisation. 5.3. Oxygen shifts. 6: Carbonylation of Methanol and Methyl Acetate.- 6.1. Acetic acid. 6.2. Process scheme Monsanto process. 6.3. Acetic anhydride. 6.4. Other systems. 7: Cobalt Catalysed Hydroformylation.- 7.1. Introduction. 7.2. Thermodynamics. 7.3. Cobalt catalysed processes. 7.4. Cobalt catalysed processes for higher alkenes. 7.5. Kuhlmann cobalt hydroformylation process. 7.6. Phosphine modified cobalt catalysts: the shell process. 7.7. Cobalt carbonyl phosphine complexes. 8: Rhodium Catalysed Hydroformylation.- 8.1. Introduction. 8.2. Triphenylphosphine asthe ligand. 8.3. Diphosphines as ligands. 8.4. Phosphites as ligands. 8.5. Diphosphites. 8.6. Asymmetric hydroformylation. 9: Alkene Oligomerisation.- 9.1. Introduction. 9.2. Shell-higher-olefins-process. 9.3. Ethene trimerisation. 9.4. Other alkene oligomerisation reactions. 10: Propene Polymerisation.- 10.1. Introduction to polymer chemistry. 10.2. Mechanistic investigations. 10.3. Analysis by 13CNMR spectroscopy. 10.4. The development of metallocene catalysts. 10.5. Agostic interactions. 10.6. The effect of dihydrogen. 10.7. Further work using propene and other alkenes. 10.8. Non-metallocene ETM catalysts. 10.9. Late transition metal catalysts. 11: Hydrocyanation of Alkenes.- 11.1. The adiponitrile process. 11.2. Ligand effects. 12: Palladium Catalysed Carbonylations of Alkenes.- 12.1. Introduction. 12.2. Polyketone. 12.3. Ligand effects on chain length. 12.4. Ethene/propene/CO terpolymers. 12.5. Stereoselective styrene/CO terpolymers. 13: Palladium Catalysed Cross-Coupling Reactions.- 13.1. Introduction. 13.2. Allylic reaction. 13.3. Heck reaction. 13.4. Cross-coupling reaction. 13.5. Heteroatom-carbon bond formation. 13.6. Suzuki reaction. 14: Epoxidation.- 14.1. Ethene and propene oxide. 14.2. Asymmetric epoxidation. 14.3. Asymmetric hydroxilation of alkenes with osmium tetroxide. 14.4. Jacobsen asymmetric ring-opening of epoxides. 14.5. Epoxidations with dioxygen. 15: Oxydation with Dioxygen.- 15.1. Introduction. 15.2. The Wacker reaction. 15.3. Wacker type reactions. 15.4. Terephthalic acid. 15.5. PPO. 16: Alkene Metathesis.- 16.1. Introduction. 16.2. The mechanism. 16.3. Reaction overview. 16.4. Well-characterised tungsten and molybdenum catalysts. 16.5. Ruthenium catalysts. 16.6. Stereochemistry. 16.7. Catalyst decomposition. 16.8. Alkynes. 16.9. Industrial applications. 17: Enantioselective Cyclopropanation.-

Piet W. N. M. Van Leeuwen. Homogeneous catalysis—understanding the art. Kluwer, Dordrecht, 2004, 407 pp; (UK). ISBN 1‐4020‐1999‐8

Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are discussed. The bibliography includes 205 references.

https://iopscience.iop.org/article/10.1070/RC2013v082n02ABEH004296/pdf

Phosphorus-containing macrocyclic compounds: synthesis and properties

Aryl- and heteroaryl-dichlorophosphines are mildly and selectively made in a one-pot synthesis in moderate to good yields starting from the respective aryl bromides or five-membered heterocycles, following lithiation with nBuLi, transmetalation with ZnCl2, and subsequently the reaction with PCl3. Selected aryl- and heteroaryl-dichlorophosphines were successfully synthesized using this reaction method and could easily be purified after isolation. The intermediate formation of the organozinc species is essential, as it prevents the formation of multiple substitution products. Important are also the reaction conditions: the usage of the proper solvent for the respective aromatic precursors and removal of the remaining salts by addition of a dioxane/pentane mixture. Depending on the solvent and steric demand of the substituent, mono- and bis-substitution products can be formed but formation also prevented. Hereby, different organozinc species might play an important role.

R. den Heeten

Papers

Bisxantphos: stereoselective synthesis and coordination behaviour of a new class of cyclic double bridged diphosphines