Remarkable solvent, porphyrin ligand, and substrate effects on participation of multiple active oxidants in manganese(III) porphyrin catalyzed oxidation reactions

Min Young Hyun, Young Dan Jo, Jun Ho Lee, Hong Gyu Lee, Hyun Min Park, In Hong Hwang, Kyeong Beom Kim, Suk Joong Lee, Cheal Kim

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Abstract

The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron-withdrawing and -donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1-octene, and ethylbenzene in various solvent systems, namely, toluene, CH 2Cl2, CH3CN, and H2O/CH 3CN (1:4). With an increase in the concentration of the easy-to-oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1 a) with electron-donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)Mn-OOC(O)R] species 2 a is the major active species. When the substrate was changed from the easy-to-oxidize one (cyclohexene) to difficult-to-oxidize ones (1-octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F20TPP)Mn-OOC(O)R] species 2 b generated from the reaction of [(F20TPP)MnCl] (1 b) with electron-withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)Mn-OOR] 2 a) depending on the concentration of the easy-to-oxidize substrate cyclohexene in all aprotic solvent systems except for CH3CN, whereas MnV=O species is the major active oxidant in the protic solvent system. With difficult-to-oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1-octene in toluene, indicating that a MnV=O intermediate generated from the heterolytic cleavage of 2 b becomes a major reactive species. We also studied the competitive epoxidations of cis-2-octene and trans-2-octene with two manganese(III) porphyrin complexes by meta-chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis- to trans-2-octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further supporting the contention that the reactions of manganese porphyrin complexes with peracids generate multiple reactive oxidizing intermediates.

Original languageEnglish
Pages (from-to)1810-1818
Number of pages9
JournalChemistry - A European Journal
Volume19
Issue number5
DOIs
Publication statusPublished - 2013 Jan 28

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Porphyrins
Oxidants
Thymidine Monophosphate
Ligands
Oxidation
Substrates
Epoxidation
Toluene
Electrons
Acids
Catalytic oxidation
Alkenes
Manganese
Oxides
manganese(III) porphyrin
cyclohexene
1-octene
peroxyphenylacetic acid
ethylbenzene

Keywords

  • manganese
  • oxidation
  • oxido ligands
  • porphyrinoids
  • solvent effects

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Remarkable solvent, porphyrin ligand, and substrate effects on participation of multiple active oxidants in manganese(III) porphyrin catalyzed oxidation reactions. / Hyun, Min Young; Jo, Young Dan; Lee, Jun Ho; Lee, Hong Gyu; Park, Hyun Min; Hwang, In Hong; Kim, Kyeong Beom; Lee, Suk Joong; Kim, Cheal.

In: Chemistry - A European Journal, Vol. 19, No. 5, 28.01.2013, p. 1810-1818.

Research output: Contribution to journalArticle

Hyun, Min Young ; Jo, Young Dan ; Lee, Jun Ho ; Lee, Hong Gyu ; Park, Hyun Min ; Hwang, In Hong ; Kim, Kyeong Beom ; Lee, Suk Joong ; Kim, Cheal. / Remarkable solvent, porphyrin ligand, and substrate effects on participation of multiple active oxidants in manganese(III) porphyrin catalyzed oxidation reactions. In: Chemistry - A European Journal. 2013 ; Vol. 19, No. 5. pp. 1810-1818.
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abstract = "The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron-withdrawing and -donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1-octene, and ethylbenzene in various solvent systems, namely, toluene, CH 2Cl2, CH3CN, and H2O/CH 3CN (1:4). With an increase in the concentration of the easy-to-oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1 a) with electron-donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)Mn-OOC(O)R] species 2 a is the major active species. When the substrate was changed from the easy-to-oxidize one (cyclohexene) to difficult-to-oxidize ones (1-octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F20TPP)Mn-OOC(O)R] species 2 b generated from the reaction of [(F20TPP)MnCl] (1 b) with electron-withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)Mn-OOR] 2 a) depending on the concentration of the easy-to-oxidize substrate cyclohexene in all aprotic solvent systems except for CH3CN, whereas MnV=O species is the major active oxidant in the protic solvent system. With difficult-to-oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1-octene in toluene, indicating that a MnV=O intermediate generated from the heterolytic cleavage of 2 b becomes a major reactive species. We also studied the competitive epoxidations of cis-2-octene and trans-2-octene with two manganese(III) porphyrin complexes by meta-chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis- to trans-2-octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further supporting the contention that the reactions of manganese porphyrin complexes with peracids generate multiple reactive oxidizing intermediates.",
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T1 - Remarkable solvent, porphyrin ligand, and substrate effects on participation of multiple active oxidants in manganese(III) porphyrin catalyzed oxidation reactions

AU - Hyun, Min Young

AU - Jo, Young Dan

AU - Lee, Jun Ho

AU - Lee, Hong Gyu

AU - Park, Hyun Min

AU - Hwang, In Hong

AU - Kim, Kyeong Beom

AU - Lee, Suk Joong

AU - Kim, Cheal

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N2 - The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron-withdrawing and -donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1-octene, and ethylbenzene in various solvent systems, namely, toluene, CH 2Cl2, CH3CN, and H2O/CH 3CN (1:4). With an increase in the concentration of the easy-to-oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1 a) with electron-donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)Mn-OOC(O)R] species 2 a is the major active species. When the substrate was changed from the easy-to-oxidize one (cyclohexene) to difficult-to-oxidize ones (1-octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F20TPP)Mn-OOC(O)R] species 2 b generated from the reaction of [(F20TPP)MnCl] (1 b) with electron-withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)Mn-OOR] 2 a) depending on the concentration of the easy-to-oxidize substrate cyclohexene in all aprotic solvent systems except for CH3CN, whereas MnV=O species is the major active oxidant in the protic solvent system. With difficult-to-oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1-octene in toluene, indicating that a MnV=O intermediate generated from the heterolytic cleavage of 2 b becomes a major reactive species. We also studied the competitive epoxidations of cis-2-octene and trans-2-octene with two manganese(III) porphyrin complexes by meta-chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis- to trans-2-octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further supporting the contention that the reactions of manganese porphyrin complexes with peracids generate multiple reactive oxidizing intermediates.

AB - The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron-withdrawing and -donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1-octene, and ethylbenzene in various solvent systems, namely, toluene, CH 2Cl2, CH3CN, and H2O/CH 3CN (1:4). With an increase in the concentration of the easy-to-oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1 a) with electron-donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)Mn-OOC(O)R] species 2 a is the major active species. When the substrate was changed from the easy-to-oxidize one (cyclohexene) to difficult-to-oxidize ones (1-octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F20TPP)Mn-OOC(O)R] species 2 b generated from the reaction of [(F20TPP)MnCl] (1 b) with electron-withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)Mn-OOR] 2 a) depending on the concentration of the easy-to-oxidize substrate cyclohexene in all aprotic solvent systems except for CH3CN, whereas MnV=O species is the major active oxidant in the protic solvent system. With difficult-to-oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1-octene in toluene, indicating that a MnV=O intermediate generated from the heterolytic cleavage of 2 b becomes a major reactive species. We also studied the competitive epoxidations of cis-2-octene and trans-2-octene with two manganese(III) porphyrin complexes by meta-chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis- to trans-2-octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further supporting the contention that the reactions of manganese porphyrin complexes with peracids generate multiple reactive oxidizing intermediates.

KW - manganese

KW - oxidation

KW - oxido ligands

KW - porphyrinoids

KW - solvent effects

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