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Unimolecular and bimolecular homolytic reactions of organochromium and organocobalt complexes. Kinetics and equilibria

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00330a027· OSTI ID:6200218
;
The rates of the reversible alkyl group transfer between Cr/sup 2 +/ and Co/sup II/(dmgBF/sub 2/)/sub 2/(H/sub 2/O)/sub n/ H/sub 2/O, pH 1-3, show a strong dependence on steric effects of the alkyl group, consistent with an S/sub H/2 mechanism. The equilibrium constants for the alkylchromium formation (Cr/sup 2 +/ + RCo(dmgBF/sub 2/)/sub 2/OH/sub 2/ = RCr/sup 2 +/ + Co(dmgBF/sub 2/)/sub 2/) are 6.43 x 10/sup -2/, 3.70 x 10/sup -3/, 2.80 x 10/sup -3/, and approx. < 10/sup -5/ for R = CH/sub 3/, C/sup 2/H/sub 5/, C/sub 6/H/sub 5/CH/sub 2/, and CH/sub 2/OCH/sub 3/, respectively. The latter reaction yields the previously unknown CH/sub 3/OCH/sub 2/Co(dmgBF/sub 2/)/sub 2/. The benzyl complex undergoes unimolecular homolysis (k = 7.6 x 10/sup -6/ s/sup -1/ at 25/sup 0/C); the bond dissociation enthalpy of its Co-C bond is 24 +/- 3 kcal/mol. The rate constant for the reverse reaction is 8.8 x 10/sup 7/ M/sup -1/ s/sup -1/. 51 references, 4 figures, 5 tables.
Research Organization:
Iowa State Univ., Ames
DOE Contract Number:
W-7405-ENG-82
OSTI ID:
6200218
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Journal Issue: 18 Vol. 106:18; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
400301 -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
ALKANES
AMINES
AQUEOUS SOLUTIONS
AROMATICS
BORON COMPLEXES
BORON COMPOUNDS
BORON FLUORIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
DATA ANALYSIS
DISPERSIONS
ENTHALPY
EQUILIBRIUM
ETHERS
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDRATES
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
KINETICS
LIGANDS
MAGNETIC RESONANCE
MIXTURES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIMES
PH VALUE
PHYSICAL PROPERTIES
REACTION KINETICS
RESONANCE
SOLUTIONS
SPECTRA
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET SPECTRA