Kinetics and mechanism of phosphine substitution for CO in (Fe sub 2 Co(CO) sub 9 (CCO)) sup minus
Journal Article
·
· Journal of the American Chemical Society; (USA)
- Northwestern Univ., Evanston, IL (USA)
Rate laws and activation parameters were determined for CO substitution of (PPN)(Fe{sub 2}Co(CO){sub 9}(CCO)) by phosphine ligands. These results along with the dependence of the reaction on the nature of the incoming ligand support an associative mechanism. Previous NMR data indicate that the phosphines selectively attack the Co metal center. Activation parameters are {Delta}H{double dagger} = +7.2 to +10.3 kcal/mol and {Delta}S{double dagger} = {minus}34.0 to {minus}45.5 cal/mol K. The activated complex is proposed to attain an open structure by breaking either a metal-metal or metal-carbon bond. An increase in solvent polarity increases the rate of ligand substitution, whereas a change in the cation from PPN{sup +} to Me{sub 4}N{sup +} has a negligible effect. The rates of reaction were influenced by both the basicity and steric properties of the phosphines.
- OSTI ID:
- 5093789
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:9; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
A mechanistic investigation of phosphine migration and substitution in (Fe sub 2 Co(CO) sub 8 (PR sub 3 )(CCO)) sup minus
Thermodynamic and activation parameters for dissociation of [CpCr(CO){sub 3}]{sub 2} and [Cp*Cr(CO){sub 3}]{sub 2} into paramagnetic monomers from {sup 1}H NMR shift and line width measurements
Water-soluble organometallic compounds. 3. Kinetic investigations of dissociative phosphine substitution processes involving water-soluble group 6 metal derivatives in miscible aqueous/organic media
Journal Article
·
Wed Apr 26 00:00:00 EDT 1989
· Journal of the American Chemical Society; (USA)
·
OSTI ID:5119462
Thermodynamic and activation parameters for dissociation of [CpCr(CO){sub 3}]{sub 2} and [Cp*Cr(CO){sub 3}]{sub 2} into paramagnetic monomers from {sup 1}H NMR shift and line width measurements
Journal Article
·
Mon Sep 06 00:00:00 EDT 1999
· Inorganic Chemistry
·
OSTI ID:20000074
Water-soluble organometallic compounds. 3. Kinetic investigations of dissociative phosphine substitution processes involving water-soluble group 6 metal derivatives in miscible aqueous/organic media
Journal Article
·
Tue Jan 05 23:00:00 EST 1993
· Inorganic Chemistry; (United States)
·
OSTI ID:6924286
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
ENERGY
EXPERIMENTAL DATA
INFORMATION
IRON COMPLEXES
KINETICS
LIGANDS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PH VALUE
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION KINETICS
STEREOCHEMISTRY
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
ENERGY
EXPERIMENTAL DATA
INFORMATION
IRON COMPLEXES
KINETICS
LIGANDS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PH VALUE
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION KINETICS
STEREOCHEMISTRY
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES