Published March 15, 1979
| Version v1
Journal article
Secondary α-hydrogen kinetic isotope effects in nucleophilic additions to ferrocenyl-stabilised carbocations
Description
The secondary α-hydrogen kinetic isotope effects upon the solvolyses of Fc2C+H (1a) and p-MeOC6H4C+HFc (1b) (Fc = ferrocenyl) in H2O, H2O-MeCN, and H2O-MeOH (ksub(f)sup(H)/ksub(f)sup(D) = ca. 0.9), and upon the acid heterolyses of the corresponding alcohols (ksub(r)sup(H)/ksub (r)sup(D) = ca. 1.1), suggest that there is appreciable C....O bond formation in the transition state for carbocation solvolysis; for additions of HO-, N3-, and BH4- to (1a), ksub(f)sup(H)/ksub(f)sup(D) = ca. 1.0, indicating 'early' carbocation-like transition states for these reactions, whereas intermediate values (ksub(f)sup(H)/ksub(f)sup(D) = ca. 0.96) are found for additions of primary amines. (author)
Additional details
Publishing Information
- Journal Title
- J. Chem. Soc. (London), Chem. Commun.
- Journal Issue
- no.6
- Series
- J. Chem. Soc. (London), Chem. Commun.
INIS
- Country of Publication
- United Kingdom
- Country of Input or Organization
- United Kingdom
- INIS RN
- 10462696
- Subject category
- S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
- Resource subtype / Literary indicator
- Numerical Data
- Descriptors DEI
- CATIONS; CHEMICAL REACTION KINETICS; DEUTERIUM; EXPERIMENTAL DATA; FERROCENE; HYDROGEN; ISOLATED VALUES; ISOTOPE EFFECTS; MOLECULAR STRUCTURE; SOLVOLYSIS
- Descriptors DEC
- CHARGED PARTICLES; CHEMICAL REACTIONS; COMPLEXES; DATA; DATA FORMS; DECOMPOSITION; DIENES; ELEMENTS; HYDROCARBONS; HYDROGEN ISOTOPES; INFORMATION; IONS; IRON COMPLEXES; ISOTOPES; KINETICS; LIGHT NUCLEI; NONMETALS; NUCLEI; NUMERICAL DATA; ODD-ODD NUCLEI; ORGANIC COMPOUNDS; POLYENES; REACTION KINETICS; STABLE ISOTOPES; TRANSITION ELEMENT COMPLEXES