Model
Digital Document
Publisher
Florida Atlantic University
Description
A study of the kinetic behavior of the oxygen atom transfer reaction of Mo2o3 (Et2dtc)2 (THF) 2I2, (I), with a variety of derivatives of pyridine N-oxides has been performed. The reaction behaves in pseudo-first-order fashion under conditions of excess N-oxide. Plots of kobs vs. [N-oxide] do not give straight lines, while plots of 1/kobs vs. 1/[N-oxide] are linear. The rate constant k is taken as the inverse of the slope of this latter plot. There is a marked dependence of the rate on the functional group in the 4-position of the pyridine ring with the relative rates -CH3 > -H > -Cl > -CN. The above observations can be used to support a mechanism in which a rapid pre-equilibrium, with a large equilibrium constant, is followed by a rate-determining breaking of the Mo-O-Mo bridge.
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