SOME DECOMPOSITION REACTIONS OF DIPEROXOTRIAMMINECHROMIUM(4)

Decomposition of Cr(NH3)3(O2)2 in 1 F HClO4 at 20–25° gives Cr(NH3)3(OH2)33+ (ca. 40%, probably the pure 1,2,3 (cis) isomer), Cr(NH3)2(OH2)43+ (ca. 35%, probably largely or wholly the cis isomer), Cr(NH3)(OH2)63+ (ca. 15%), and Cr(OH2)63+ (ca. 10%). In 1FNaOH at 102° the diperoxo compound decomposes ca. 95% via a path forming CrO42−, NH3, O2, and H2O (or possibly some H2O2); the other ca. 5% of reaction produces CrO42− and a nitrogen-containing species which is neither NH3 nor NO2 - and which slowly reacts with the CrO42− or which catalyzes the oxidation of H2O by CrO42−. Explosion of the diperoxo compound by sudden heating occurs ca. 90% via formation of Cr2O3, NH3, and O2; the other ca. 10% of reaction yields Cr2O3, N2O, N2, and H2O. © 1968, American Chemical Society. All rights reserved.