Four-center cyclic transition states and their associated deuterium kinetic isotope effects: hydrogenolysis of n-octyllithium

The temperature dependence of the kinetic isotopic effect associated with a transition state in which the requirement of a significantly nonlinear hydrogen transfer is reasonably unequivocal was studied. The hydrogenolysis of n-octyllithium proceeds readily and quantitatively in decane solution under an ambient pressure of hydrogen and at temperatures <100/sup 0/C. The kinetics for this reaction, which is pseudo first order in n-octyllithium, are summarized. Also summarized are the relevant data obtained under competitive conditions. Within experimental error, both independent and competitive reactions exhibit equivalent temperature dependencies.