The secondary kinetic isotope effects for the hydride transfer reactions from aliphatic alcohols to four carbocations (NAD+ models) in acetonitrile were determined. The results suggest that the hydride transfer takes place by tunneling and that the rehybridizations of both donor and acceptor carbons lag behind the H-tunneling. This is quite contrary to the observations in alcohol dehydrogenases where the importance of enzyme motions in catalysis is manifested.
|Commitee:||Luesse, Sarah, Wei, Chin-Chuan|
|School:||Southern Illinois University at Edwardsville|
|School Location:||United States -- Illinois|
|Source:||MAI 52/04M(E), Masters Abstracts International|
|Subjects:||Organic chemistry, Physical chemistry|
|Keywords:||Alcohol dehydrogenase, Hydride transfer reactions, Kinetic isotope effect, Quantom tunneling effect|
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