Bulletin 600
The Chemistry and Catalytic Properties of Cobalt and Iron Carbonyls
| Section
1 386kb pdf |
Summary | |||
| Introduction | ||||
| Acknowledgements | ||||
| Section
2 1312 kb pdf |
Structure and properties of metal carbonyls | |||
| Composition and effective atomic number of metal carbonyls and the nature of metal-carbon-oxygen bond | ||||
| Spectra and structures of cobalt carbonyls | ||||
| Dicobalt octacarbonyl, Co2(CO)8 | ||||
| Tetracobalt dodecacarbonyl, Co4(CO)12 | ||||
| Cobalt hydrocarbonyl, H Co(CO)4, and cobalt deuterocarbonyl, D Co(CO)4 | ||||
| Proton magnetic resonance of H Co(CO)4 | ||||
| Cobalt carbonyl anion, [Co(CO)4] | ||||
| Section
3 1785kb pdf |
Dicobalt octacarbonyl | |||
| Preparation | ||||
| Analysis | ||||
| Reactions with bases | ||||
| Formation of cobalt carbonyl anion by electron transfer | ||||
| Mechanism of the reaction | ||||
| Reaction with alkynes | ||||
| The infrared spectra of acetylenic dicobalt hexacarbonyls | ||||
| Structure of acetylenic dicobalt hexacarbonyls | ||||
| Physical constants of diphenyl-acetylene dicobalt hexacarbonyl | ||||
| Stability of acetylenic dicobalt hexacarbonyls | ||||
| Section
4 1631kb pdf |
Cobalt hydrocarbonyl | |||
| Preparation | ||||
| Stability | ||||
| Reactions of H Co(CO)4 | ||||
| Dissociation of iron pentacarbonyl in amines | ||||
| Dissociation in piperidine | ||||
| Effect of amine structure on the dissociation of Fe(CO)5 | ||||
| Mechanism | ||||
| The iron pentacarbonyl-aqueous alkali system | ||||
| Section
5 1233kb pdf |
The iron carbonyl-acetylene complex Fe2C10H4O8 | |||
| Structure | ||||
| Preparation and properties | ||||
| Iron hydrocarbonyl, H2Fe(CO)4 | ||||
| Preparation | ||||
| Decomposition in the gas phase | ||||
| Decomposition in solution | ||||
| Reaction with acetone and 1-hexene | ||||
| Section
6 1622kb pdf |
Reactions catalyzed by the cobalt carbonyls | |||
| The oxo reaction | ||||
| Introduction | ||||
| The principal reaction | ||||
| Commercial charge stocks and products | ||||
| Scope and limitations of the reaction | ||||
| Other reactions occurring under oxo conditions | ||||
| Hydrogenation of olefins | ||||
| Polymerization of olefins | ||||
| Hydrogenation of aldehydes | ||||
| Acetal formation | ||||
| Aldol formation | ||||
| Ketones formation | ||||
| Kinetics | ||||
| Effect of partial pressures of carbon monoxide and hydrogen | ||||
| Effect of temperature | ||||
| Effect of solvent | ||||
| Effect of bases Kinetics at low pressures (under 100 atm.) | ||||
| Section
7 2296kb pdf |
Mechanism of hydroformylation | |||
| Function of carbonyls | ||||
| Early postulations as to mechanism | ||||
| Later work | ||||
| Nature of the olefin in the intermediate complexes | ||||
| Hydrogenation of organic compounds with synthesis gas | ||||
| Homogeneous character of the hydrogenation | ||||
| Hydrogenation of double bonds in conjugated systems | ||||
| a,ß-Unsaturated aldehydes and ketones | ||||
| Conjugated diolefins and styrenes | ||||
| Polynuclear aromatic compounds | ||||
| Reduction of aromatic alcohols and ketones | ||||
| Hydrogenation of thiophene and substituted thiophene | ||||
| Section
8 1680kb pdf |
Lengthening the carbon chain (homologation) of alcohols | |||
| Rearrangements under hydroformylation conditions | ||||
| The reaction of acetylenes | ||||
| Polymerization of acetylenes by dicobalt octacarbonyl | ||||
| Reactions of acetylene under hydroformylation conditions | ||||
| Reaction of 1-pentyne under hydroformylation conditions | ||||
| Reaction of diphenylacetylene under hydroformylation conditions | ||||
| Stoichiometric reaction of acetylene with cobalt hydrocarbonyl | ||||
| Some catalytic properties of iron carbonyls | ||||
| 824kb pdf | Bibliography | |||