Secondary. cap alpha. -deuterium kinetic isotope effects in solvolyses of ferrocenylmethyl acetate and benzoate in ethanol
- 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), Vol. 47:26
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ISOTOPE EFFECTS
IRON COMPLEXES
SOLVOLYSIS
CHEMICAL REACTION KINETICS
ACETATES
CONDENSED CYCLOALKANES
EXPERIMENTAL DATA
ALKANES
CARBOXYLIC ACID SALTS
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKANES
DATA
DECOMPOSITION
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400202* - Isotope Effects
Isotope Exchange
& Isotope Separation