Disproportionation of Aquachromyl(IV) Ion by Hydrogen Abstraction from Coordinated Water

In aqueous solutions, the aquachromyl(IV) ion, Cr(aq)O(2+), disproportionates to Cr(aq)(3+) and HCrO(4)(-). The reaction exhibits second-order kinetics with an inverse [H(+)] dependence, -d[Cr(aq)O(2+)]/dt = 38.8[Cr(aq)O(2+)](2)[H(+)](-1) at 25 degrees C. The combination of the rate law and substantial kinetic isotope effect, k(H)/k(D) = 6.9, suggests a mechanism whereby a hydrogen atom is abstracted from a coordinated molecule of water or hydroxo group within a singly deprotonated transition state. The buildup of chromate is more complicated and somewhat slower than the loss of chromyl, suggesting the involvement of intermediates.