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Bulletin 600

The Chemistry and Catalytic Properties of Cobalt and Iron Carbonyls

Cover Page

Contents

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,-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