A detailed kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by Pt(II) complexes is reported. The two systems analyzed were (diphoe)Pt(CF3)(OH)/1-octene/H2O2/H2O/THF and [(diphoe)Pt(CF3)(CH2Cl2)]BF4/1-octene/ H2O2/H2O/CH2C12. Rate data were determined with GLC from epoxide formed vs time plots. Evidence for many of the organometallic intermediates and the individual steps involved was gained from IR studies, 19F NMR studies, and especially designed experiments including studies of the acidity effect. In both cases the kinetic analysis suggests a mechanism in which the actual oxidant is a PtOOH species that interacts with a Pt-olefin complex in the oxygen-transfer step (second-order dependence on platinum). © 1988, American Chemical Society. All rights reserved.
Kinetic study of the epoxidation of 1-Octene with hydrogen peroxide catalyzed by platinum(II) complexes. Evidence of the involvement of two metal species in the oxygen-transfer step
PINNA, Francesco;STRUKUL, Giorgio
1988
Abstract
A detailed kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by Pt(II) complexes is reported. The two systems analyzed were (diphoe)Pt(CF3)(OH)/1-octene/H2O2/H2O/THF and [(diphoe)Pt(CF3)(CH2Cl2)]BF4/1-octene/ H2O2/H2O/CH2C12. Rate data were determined with GLC from epoxide formed vs time plots. Evidence for many of the organometallic intermediates and the individual steps involved was gained from IR studies, 19F NMR studies, and especially designed experiments including studies of the acidity effect. In both cases the kinetic analysis suggests a mechanism in which the actual oxidant is a PtOOH species that interacts with a Pt-olefin complex in the oxygen-transfer step (second-order dependence on platinum). © 1988, American Chemical Society. All rights reserved.
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