Abstract
AbstractHomogeneous hydrolytic oxidation of hypophosphite in HCl solutions catalyzed by Rh(III)/Rh(I) has been studied by cyclic voltammetry and on‐line mass spectrometry. The effect of H/D substitution in both hypophosphite and water on the kinetics of the process has been studied. A deuterium tracer evidenced hydrogen to evolve entirely from water in the course of Rh(III)/Rh(I)‐catalyzed homogeneous oxidation of hypophosphite. No kinetic H/D isotope effect (kH/kD) has been found for H/D substitution in hypophosphite. kH/kD = 1.4 ± 0.1 has been found for H/D substitution in water. Possible transformations in both structure and composition of Rh(III) and Rh(I) complexes occurring during homogeneous catalytic hypophosphite oxidation by water are discussed.
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