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Preparation of a series of (imidazole)pentaaquachromium(III) complexes and kinetics of their reduction by 1-hydroxy-1-methylethyl radicals

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00003a024· OSTI ID:5977520
;  [1]; ; ;  [2]
  1. Iowa State Univ., Ames (USA)
  2. Rudjer Boskovic Inst., Croatia (Yugoslavia)
A series of (imidazole)pentaaquachromium(III) complexes, (H{sub 2}O){sub 5}Cr(Im-X,Y){sup 3+} were prepared and characterized in acidic aqueous solution. These complexes are reduced by {sup {center dot}}C(CH{sub 3}){sub 2}OH radicals with rate constants that vary with substituents on the imidazole ring. At 25C the values of the rate constants, k/10{sup 5} L mol{sup {minus}1} s{sup {minus}1} (X,Y), are 1.1 (1-CH{sub 3}, H), 2.1 (2-CH{sub 3}, H), 3.8 (4-CH{sub 3}, H), 6.6 (H, H), 7.2 (4-CH{sub 3}, 5-CONH{sub 2}), and 16 (4-Cl, 5-Cl). A mechanism is proposed whereby the initial electron transfer takes place at coordinated imidazole, followed by a rapid intramolecular electron transfer to yield Cr(H{sub 2}O){sub 6}{sup 2+} and X,Y-ImH{sup +}.
OSTI ID:
5977520
Journal Information:
Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:3; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English