Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions

Youngrae Jo; Jamespandi Annaraj; Mi Sook Seo; Yong Min Lee; Sung Yeon Kim; Jaeheung Cho; Wonwoo Nam

doi:10.1016/j.jinorgbio.2008.08.008

Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions

Youngrae Jo, Jamespandi Annaraj, Mi Sook Seo, Yong Min Lee, Sung Yeon Kim, Jaeheung Cho, Wonwoo Nam

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

58 Scopus citations

Abstract

A mononuclear cobalt(III)-peroxo complex bearing a macrocyclic tetradentate N₄ ligand, [Co^III(TMC)(O₂)]⁺ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was generated in the reaction of [Co^II(TMC)]²⁺ and H₂O₂ in the presence of triethylamine in CH₃CN. The reactivity of the cobalt(III)-peroxo complex was investigated in aldehyde deformylation with various aldehydes and compared with that of iron(III)- and manganese(III)-peroxo complexes, such as [Fe^III(TMC)(O₂)]⁺ and [Mn^III(TMC)(O₂)]⁺. In this reactivity comparison, the reactivities of metal-peroxo species were found to be in the order of [Mn^III(TMC)(O₂)]⁺ > [Co^III(TMC)(O₂)]⁺ > [Fe^III(TMC)(O₂)]⁺. A positive Hammett ρ value of 1.8, obtained in the reactions of [Co^III(TMC)(O₂)]⁺ and para-substituted benzaldehydes, demonstrates that the aldehyde deformylation by the cobalt(III)-peroxo species occurs via a nucleophilic reaction.

Original language	English
Pages (from-to)	2155-2159
Number of pages	5
Journal	Journal of Inorganic Biochemistry
Volume	102
Issue number	12
DOIs	https://doi.org/10.1016/j.jinorgbio.2008.08.008
State	Published - Dec 2008

Keywords

Aldehyde deformylation
Bioinorganic chemistry
Cobalt-peroxo
O-O activation
Oxidation

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10.1016/j.jinorgbio.2008.08.008

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title = "Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions",

abstract = "A mononuclear cobalt(III)-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [CoIII(TMC)(O2)]+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was generated in the reaction of [CoII(TMC)]2+ and H2O2 in the presence of triethylamine in CH3CN. The reactivity of the cobalt(III)-peroxo complex was investigated in aldehyde deformylation with various aldehydes and compared with that of iron(III)- and manganese(III)-peroxo complexes, such as [FeIII(TMC)(O2)]+ and [MnIII(TMC)(O2)]+. In this reactivity comparison, the reactivities of metal-peroxo species were found to be in the order of [MnIII(TMC)(O2)]+ > [CoIII(TMC)(O2)]+ > [FeIII(TMC)(O2)]+. A positive Hammett ρ value of 1.8, obtained in the reactions of [CoIII(TMC)(O2)]+ and para-substituted benzaldehydes, demonstrates that the aldehyde deformylation by the cobalt(III)-peroxo species occurs via a nucleophilic reaction.",

keywords = "Aldehyde deformylation, Bioinorganic chemistry, Cobalt-peroxo, O-O activation, Oxidation",

author = "Youngrae Jo and Jamespandi Annaraj and Seo, {Mi Sook} and Lee, {Yong Min} and Kim, {Sung Yeon} and Jaeheung Cho and Wonwoo Nam",

year = "2008",

month = dec,

doi = "10.1016/j.jinorgbio.2008.08.008",

language = "English",

volume = "102",

pages = "2155--2159",

journal = "Journal of Inorganic Biochemistry",

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T1 - Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions

AU - Jo, Youngrae

AU - Annaraj, Jamespandi

AU - Seo, Mi Sook

AU - Lee, Yong Min

AU - Kim, Sung Yeon

AU - Cho, Jaeheung

AU - Nam, Wonwoo

PY - 2008/12

Y1 - 2008/12

N2 - A mononuclear cobalt(III)-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [CoIII(TMC)(O2)]+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was generated in the reaction of [CoII(TMC)]2+ and H2O2 in the presence of triethylamine in CH3CN. The reactivity of the cobalt(III)-peroxo complex was investigated in aldehyde deformylation with various aldehydes and compared with that of iron(III)- and manganese(III)-peroxo complexes, such as [FeIII(TMC)(O2)]+ and [MnIII(TMC)(O2)]+. In this reactivity comparison, the reactivities of metal-peroxo species were found to be in the order of [MnIII(TMC)(O2)]+ > [CoIII(TMC)(O2)]+ > [FeIII(TMC)(O2)]+. A positive Hammett ρ value of 1.8, obtained in the reactions of [CoIII(TMC)(O2)]+ and para-substituted benzaldehydes, demonstrates that the aldehyde deformylation by the cobalt(III)-peroxo species occurs via a nucleophilic reaction.

AB - A mononuclear cobalt(III)-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [CoIII(TMC)(O2)]+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was generated in the reaction of [CoII(TMC)]2+ and H2O2 in the presence of triethylamine in CH3CN. The reactivity of the cobalt(III)-peroxo complex was investigated in aldehyde deformylation with various aldehydes and compared with that of iron(III)- and manganese(III)-peroxo complexes, such as [FeIII(TMC)(O2)]+ and [MnIII(TMC)(O2)]+. In this reactivity comparison, the reactivities of metal-peroxo species were found to be in the order of [MnIII(TMC)(O2)]+ > [CoIII(TMC)(O2)]+ > [FeIII(TMC)(O2)]+. A positive Hammett ρ value of 1.8, obtained in the reactions of [CoIII(TMC)(O2)]+ and para-substituted benzaldehydes, demonstrates that the aldehyde deformylation by the cobalt(III)-peroxo species occurs via a nucleophilic reaction.

KW - Aldehyde deformylation

KW - Bioinorganic chemistry

KW - Cobalt-peroxo

KW - O-O activation

KW - Oxidation

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U2 - 10.1016/j.jinorgbio.2008.08.008

DO - 10.1016/j.jinorgbio.2008.08.008

M3 - Article

C2 - 18842302

AN - SCOPUS:55349109606

SN - 0162-0134

VL - 102

SP - 2155

EP - 2159

JO - Journal of Inorganic Biochemistry

JF - Journal of Inorganic Biochemistry

IS - 12

ER -

Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions

Abstract

Keywords

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