Homolytic decomposition of tertiary organochromium(III) complexes and evidence for their decomposition via reactions with aliphatic free radicals. A pulse radiolysis study

Article abstract of DOI:10.1021/ic00141a028

The rates of homolytic decomposition of Cr-C(CH₃)₂OH²⁺-, Cr-C(CH₃)₂CO₂H²+, and Cr-C(CH₃)₂CN²⁺ are 0.15 s^-1, 4 s^-1, and 10⁴ < k < 10^-6 s^-1, respectively. The reaction of some aliphatic free radicals,·R with Cr^III-R complexes is very fast, K₃ ≥ 10⁸ M^-1 S^-1. The rate of reaction of Cr²⁺(aq) with H₂O₂ is k16 = (3.7 ±0.7) × 10⁴ M^-1 s^-1 in good accord with the literature value. These results are discussed in detail.