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Updated: Aug 17, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Novel Pathways in the Reactions of Superoxometal Complexes
A. Bakac1, Tae-Jin Won, J. H. Espenson
1Chemistry Department and Ames Laboratory, Iowa State University, Ames, Iowa 50011.
Abstract:
The reaction of a 1:1 mixture of (H(2)O)(5)Cr((16)O(2))(2+) and (H(2)O)(5)Cr((18)O(2))(2+) at pH 1 did not yield measurable amounts of (16)O(18)O. This result rules out a Russell-type mechanism (2(H(2)O)(5)CrO(2)(2+) --> 2(H(2)O)(5)CrO(2+) + O(2)) for the bimolecular decomposition reaction. Evidence is presented in support of unimolecular (S(H)1) and bimolecular (S(H)2) homolyses as initial steps in the decomposition of (H(2)O)(5)CrO(2)(2+) in strongly acidic solutions (pH = 1). In the pH range 4-5, (H(2)O)(5)CrO(2)(2+) undergoes hydrolysis-induced disproportionation to (H(2)O)(5)CrO(2)H(2+), Cr(H(2)O)(6)(3+) and O(2). The first step produces HO(2)(*)/O(2)(*)(-), which in further reaction with (H(2)O)(5)CrO(2)(2+) yields the observed products.
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