Imbalanced tunneling ready states in alcohol dehydrogenase model reactions: rehybridization lags behind H-tunneling.
نویسندگان
چکیده
The secondary kinetic isotope effects for the hydride transfer reactions from aliphatic alcohols to two 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.
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ورودعنوان ژورنال:
- Chemical communications
دوره 48 92 شماره
صفحات -
تاریخ انتشار 2012