1996
DOI: 10.1021/ic950950z
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Reactivity of the Coordinated Hydroperoxo Ligand

Abstract: The reactivity of the hydroperoxo complex [Co(CN)(5)OOH](3)(-) has been studied in aqueous solution. The complex undergoes acid-catalyzed aquation (k = 1.89(5) x 10(-)(2) s(-)(1), pK(a) = 5.21(4), T = 20 degrees C, I = 0.1 M). Assuming an I(d) mechanism, this allows the relative affinity for Co(III) to be deduced as H(2)O(2) < H(2)O < HO(2)(-) and implies H(2)O(2) to be a very weak ligand. At neutral pH the hydroperoxo complex effects efficient oxygen atom transfer to L-methionine to give an intermediate ident… Show more

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Cited by 38 publications
(34 citation statements)
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“…Cobalt(II) bispidine complexes in general are air stable (69,166,167,189). This finding is unusual in cobalt-amine chemistry, where the cobalt(II)-O 2 (H 2 O 2 ) coordination chemistry is dominated by the formation of m-peroxo and m-superoxo dicobalt(III) complexes and their hydrolysis to mononuclear cobalt(III) compounds (328); in addition, there are few reports on mononuclear cobalt(II) and cobalt(III) hydroperoxo and peroxo complexes (328)(329)(330)(331)(332)(333)(334). The exceptionally high redox potentials, in line with the low ligand fields (see Table VIII) are the result of the rigid bispidine ligands with a preference for relatively large metal ions (189,199).…”
Section: Oxygenation Of Copper(i) Reactions Between Copper Proteins mentioning
confidence: 99%
“…Cobalt(II) bispidine complexes in general are air stable (69,166,167,189). This finding is unusual in cobalt-amine chemistry, where the cobalt(II)-O 2 (H 2 O 2 ) coordination chemistry is dominated by the formation of m-peroxo and m-superoxo dicobalt(III) complexes and their hydrolysis to mononuclear cobalt(III) compounds (328); in addition, there are few reports on mononuclear cobalt(II) and cobalt(III) hydroperoxo and peroxo complexes (328)(329)(330)(331)(332)(333)(334). The exceptionally high redox potentials, in line with the low ligand fields (see Table VIII) are the result of the rigid bispidine ligands with a preference for relatively large metal ions (189,199).…”
Section: Oxygenation Of Copper(i) Reactions Between Copper Proteins mentioning
confidence: 99%
“…In the presence of an excess of the acid co-catalyst, pathway B becomes the dominant one leading to the formation of the metallo-acylperoxo intermediate (I) by nucleophilic attack of a molecule of the acid to the oxygen atom near the metal and loss of a water molecule aided by a second molecule of the acid. This kind of attack was already suggested to explain the formation of intermediate (I) by organic acids[19][20] and the oxidation of sulphur compounds by co-ordinated hydroperoxo complexes[21].…”
mentioning
confidence: 86%
“…This reactivity with acids, in which the oxygen-oxygen bond is cleaved in both cases, stands in contrast to the reactivity of previously reported hydroperoxo complexes, which are observed to release H 2 O 2 upon protonolysis. 24,28,39 We have considered the possibility here that H 2 O 2 is initially formed, followed by rapid disproportionation to H 2 O and O 2 . However, after treating 2 with acid, immediate addition of N,N-diethyl-pphenylenediamine (DPD), which is oxidized by H 2 O 2 and other oxygen-containing oxidants, 40 gave no evidence for the formation of the stable, bright pink N,N-diethyl-p-phenylenediamine radical (DPD˙).…”
Section: Paper Dalton Transactionsmentioning
confidence: 99%
“…Oxygen-atom-transfer reactions are among the most prevalent. [24][25][26][27][28][29][30] Oxygenation of phosphines to phosphine oxides, sulphides to sulphoxides, olefins to epoxides or carbonyl compounds, and benzaldehyde to benzoic acid has been promoted by late metal hydroperoxo and alkylperoxo complexes. Although acidolysis reactions of coordinated hydroperoxos are less studied, there are several examples of hydrogen or alkyl peroxide liberation upon treatment of a hydroperoxo or alkylperoxo complex with acid.…”
Section: Introductionmentioning
confidence: 99%