Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions
The synthesis and characterizations of some new eta/sup 5/-heterocyclic manganese tricarbonyl complexes are described. Kinetic studies are reported for CO substitution reactions of these nitrogen family eta/sup 5/-dimethylheterocyclic manganese tricarbonyl complexes. The results show that only the N-heterocycle compounds undergo CO substitution by phosphorus nucleophiles. These results are attributed to the greater electronegativity of N than that of C, P, or As. Both tricarbonyl(eta/sup 5/-3,4-dimethylpyrrolyl)manganese(I) and tricarbonyl(eta/sup 5/-2,5-dimethylpyrrolyl)manganese(I) substitute CO by an associative pathway in which the reaction rates are first order in concentration of metal complex and first order in concentration of entering nucleophile. The former compound also substitutes CO by a pathway that is independent of the concentration of incoming nucleophile. The second-order pathway is believed to involve a ring-slippage (eta/sup 5/ ..-->.. eta/sup 3/ ..-->.. eta/sup 5/) mechanism, whereas the first order pathway appears to involve a ligand-dissociation mechanism.
- Research Organization:
- Northwestern Univ., Evanston, IL
- OSTI ID:
- 5675140
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 109:24
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON MONOXIDE
CHEMICAL REACTIONS
CARBONYLS
CHEMICAL PREPARATION
MANGANESE COMPLEXES
ABSORPTION SPECTROSCOPY
ACTIVATION ENERGY
CARBON 13
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
HYDROGEN 1
NUCLEAR MAGNETIC RESONANCE
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON OXIDES
CHALCOGENIDES
COMPLEXES
DATA
ENERGY
EVEN-ODD NUCLEI
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
RESONANCE
SPECTROSCOPY
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties