Synthesis of eta/sup 5/-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on CO substitution reactions
Journal Article
·
· J. Am. Chem. Soc.; (United States)
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), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:24; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Dynamic NMR studies of restricted arene rotation in the chromiu tricarbonyl thiophene and selenophene complexes
Reaction of phenyl-containing N-substituted 1,3-oxazolidines and 1,3-oxazinanes with triammine(tricarbonyl)chromium
Chromium tricarbonyl facilitated nucleophilic aromatic substitution by metal carbonyl anions: the synthesis and molecular structure of a new class of bimetallic /pi/-arene complexes
Thesis/Dissertation
·
Fri May 27 00:00:00 EDT 1994
·
OSTI ID:10190002
Reaction of phenyl-containing N-substituted 1,3-oxazolidines and 1,3-oxazinanes with triammine(tricarbonyl)chromium
Journal Article
·
Thu Aug 15 00:00:00 EDT 2019
· Russian Chemical Bulletin
·
OSTI ID:22943125
Chromium tricarbonyl facilitated nucleophilic aromatic substitution by metal carbonyl anions: the synthesis and molecular structure of a new class of bimetallic /pi/-arene complexes
Journal Article
·
Mon Aug 01 00:00:00 EDT 1988
· Organometallics; (United States)
·
OSTI ID:5975994
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
ACTIVATION ENERGY
CARBON 13
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
ENERGY
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
MANGANESE COMPLEXES
NUCLEAR 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
ABSORPTION SPECTROSCOPY
ACTIVATION ENERGY
CARBON 13
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
ENERGY
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
MANGANESE COMPLEXES
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
RESONANCE
SPECTROSCOPY
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES