Secondary. cap alpha. -deuterium kinetic isotope effects in solvolyses of ferrocenylmethyl acetate and benzoate in ethanol
Journal Article
·
· J. Org. Chem.; (United States)
- Univ. of Zagreb, Yugoslavia
Secondary ..cap alpha..-deuterium kinetic isotope effects (KIE) in solvolyses of ferrocenyldideuteriomethyl acetate and benzoate were determined in 96% (v/v) ethanol, at 25/sup 0/C, as k/sub H//k/sub D/ = 1.24 and 1.26, respectively. The KIEs were also determined in the presence of 0.1 mol dm/sup -3/ lithium perchlorate: the k/sub H//k/ sub D/ values were 1.23 and 1.22 for acetate and benzoate complexes, respectively. The maximum KIE for the C-O bond cleavage of a primary substrate is as large as, or larger than, that of secondary derivatives, which is estimated to be 1.23 per deuterium. The measured KIE of about 12% per D therefore represents a strongly reduced effect relative to its maximum. The solvolyses exhibit ''a special salt effect''. This effect indicates the presence of solvent-separated ion pairs and the return to tight pairs. As the maximum KIE is expected in solvolyses involving transformation of one type of ion pair into another, the strongly reduced ..cap alpha..-D KIE supports the structure involving direct participation of electrons that in the ground state are localized at the iron atom. The alkyl-oxygen cleavage is accompanied by 10-15% acyl-oxygen cleavage.
- OSTI ID:
- 6310021
- Journal Information:
- J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 47:26; ISSN JOCEA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Secondary deuterium isotope effects for certain acyl transfer reactions of phenyl formates
Secondary Deuterium Isotope Effects in the Reactions of Carboxylic Acid Derivatives
What is the effect of variations optimization of the transition state on. alpha. -deuterium secondary kinetic isotope effects A prototype: CD sub 3 H + H r reversible CD sub 3 + H sub 2
Journal Article
·
Tue Jan 02 23:00:00 EST 1979
· J. Am. Chem. Soc.; (United States)
·
OSTI ID:6299353
Secondary Deuterium Isotope Effects in the Reactions of Carboxylic Acid Derivatives
Journal Article
·
Mon Dec 19 23:00:00 EST 1960
· Journal of the American Chemical Society
·
OSTI ID:4118460
What is the effect of variations optimization of the transition state on. alpha. -deuterium secondary kinetic isotope effects A prototype: CD sub 3 H + H r reversible CD sub 3 + H sub 2
Journal Article
·
Wed Aug 15 00:00:00 EDT 1990
· Journal of the American Chemical Society; (USA)
·
OSTI ID:6428335
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ACETATES
ALKANES
CARBOXYLIC ACID SALTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CONDENSED CYCLOALKANES
CYCLOALKANES
DATA
DECOMPOSITION
DEUTERIUM
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
IRON COMPLEXES
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
SOLVOLYSIS
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ACETATES
ALKANES
CARBOXYLIC ACID SALTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CONDENSED CYCLOALKANES
CYCLOALKANES
DATA
DECOMPOSITION
DEUTERIUM
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
IRON COMPLEXES
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
SOLVOLYSIS
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES