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Title: Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions

Abstract

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.

Authors:
;
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL
OSTI Identifier:
5675140
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 109:24
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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

Citation Formats

Kershner, D L, and Basolo, F. Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions. United States: N. p., 1987. Web. doi:10.1021/ja00258a024.
Kershner, D L, & Basolo, F. Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions. United States. https://doi.org/10.1021/ja00258a024
Kershner, D L, and Basolo, F. 1987. "Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions". United States. https://doi.org/10.1021/ja00258a024.
@article{osti_5675140,
title = {Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions},
author = {Kershner, D L and Basolo, F},
abstractNote = {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.},
doi = {10.1021/ja00258a024},
url = {https://www.osti.gov/biblio/5675140}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:24,
place = {United States},
year = {Wed Nov 25 00:00:00 EST 1987},
month = {Wed Nov 25 00:00:00 EST 1987}
}