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Kinetic isotope effect study of reductions of benzophenone with complex metal hydrides

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00281a032· OSTI ID:6995480
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Carbon-14 and deuterium kinetic isotope effects were determined for reductions of benzophenone with NaBH/sub 4/, LiBH/sub 4/, and LiAlH/sub 4/ at 25.0/sup 0/C. The observed /sup 12/k//sup 14/k at the carbonyl carbon and k/sub H4//k/sub D4/ of the reducing agents were 1.066 and 0.75, 1.043 and 1.089 and 1.024 and 1.10, respectively, for NaBH/sub 4/, LiBH/sub 4/ and LiAlH/sub 4/ reductions. Kinetic isotope effect calculations with various transition-state models suggested that the extent of hydride transfer from Al or B to the carbonyl carbon is increasing in the order LiAlH/sub 4/ (0.35) < LiBH/sub 4/ (0.55) < NaBH/sub 4/ (0.75). Nucleophilic solvent participation to the BH/sub 4/ moiety is weak if present for the SBH reduction.

Research Organization:
Osaka Univ., Japan
OSTI ID:
6995480
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:21; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
&amp; Isotope Separation
ALKALI METAL COMPLEXES
ALUMINIUM COMPOUNDS
ALUMINIUM HYDRIDES
BENZOPHENONE
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
BORON COMPOUNDS
BORON HYDRIDES
CARBON 14
CARBON ISOTOPES
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DEUTERIUM
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KETONES
KINETICS
LIGHT NUCLEI
LITHIUM COMPLEXES
MEDIUM TEMPERATURE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
RADIOISOTOPES
REACTION KINETICS
REDUCTION
SODIUM COMPLEXES
STABLE ISOTOPES
YEARS LIVING RADIOISOTOPES