Kinetic isotope effects normal temperature dependence

Interestingly, in a comparison of the CD3 and CHj carbenes, an unusual temperature dependence of the kinetic isotope effect was observed. In contrast to typical reactions, the ratio of rates of H versus D shift, k /ko, actually increased as temperature was raised. In fact, k was measured to be larger than k at 248 K. It was suggested that these results required a normal temperature dependence of the isotope effect for the classical component of the reaction, but an unusual diminished isotope effect for the QMT reaction. 

Kinetic complexity definition, 43 Klinman s approach, 46 Kinetic isotope effects, 28 for 2,4,6-collidine, 31 a-secondary, 35 and coupled motion, 35, 40 in enzyme-catalyzed reactions, 35 as indicators of quantum tunneling, 70 in multistep enzymatic reactions, 44-45 normal temperature dependence, 37 Northrop notation, 45 Northrop s method of calculation, 55 rule of geometric mean, 36 secondary effects and transition state, 37 semiclassical treatment for hydrogen transfer,... 

This mechanism clearly implicated alkane complexes as precursors to C-H activation but the IR absorptions of [Cp Rh(CO)Kr] and [Cp Rh(CO)(C6Hi2)] were not resolved and were presumed to be coincident. The temperature dependent data gave values of AH = 18 (or 22) kj mol for the unimolecular C-H (or C-D) activation step representing a normal kinetic isotope effect, kn/fco 10- However, an inverse equilibrium isotope effect (K /Kq 0.1) was found for the slightly exothermic pre-equilibrium displacement of Kr by CoHn/C Dn implying that C6Dj2 binds more strongly to the rhodium center than does C Hn-... 

In a separate study, kinetic isotope effects were determined for the individual steps in methane loss from tungstanocene methyl hydride. These results were combined with theoretical studies that produced a complete picture for understanding isotope effects in terms of the contributing factors (zero point energy, mass moment of inertia, and excitation terms). The conclusion was that it is possible to observe either inverse or normal isotope effects, depending on the temperature at which the study is conducted. ... 

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