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Catalytic oxidation of the (hydroxymethyl)chromium(III) ion by the superoxochromium(III) ion. [CrO sub 2 sup 2+]

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00022a006· OSTI ID:7017608
; ;  [1]
  1. Iowa State Univ., Ames (United States)

The superoxochromium(III) ion, CrO{sub 2}{sup 2+}, is an efficient catalyst for autoxidation of the (hydroxymethyl)chromium(III) ion, CrCH{sub 2}OH{sup 2+}, in aqueous solution. The reaction involves one-electron oxidation of CrCH{sub 2}OH{sup 2+} by CrO{sub 2}{sup 2+}, k = 137 M{sup {minus} 1} s{sup {minus} 1}, to yield Cr{sup 2+}, CH{sub 2}O, and the novel (hydroperoxo)chromium(III) ion, CrO{sub 2}H{sup 2+}. The Cr{sup 2+} produced reacts rapidly with O{sub 2} to regenerate the catalyst, CrO{sub 2}{sup 2+}. When oxygen is depleted, the Cr{sup 2+} reacts instead with CrO{sub 2}{sup 2+} to produce the chromyl(IV) ion, CrO{sup 2+}. This initiates a chain reaction that rapidly consumes the remaining CrO{sub 2}{sup 2+} and a stoichiometric amount of CrCH{sub 2}OH{sup 2+}.

OSTI ID:
7017608
Journal Information:
Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:22; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English