Sc 3+ (or HClO 4 ) Activation of a Nonheme Fe III -OOH Intermediate for the Rapid Hydroxylation of Cyclohexane and Benzene

Subhasree Kal, Apparao Draksharapu, Larry Que

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

[Fe(β-BPMCN)(CH 3 CN) 2 ] 2+ (1, BPMCN = N,N′-bis(pyridyl-2-methyl)-N,N′-dimethyl-trans-1,2-diaminocyclo-hexane) is a relatively poor catalyst for cyclohexane oxidation by H 2 O 2 and cannot perform benzene hydroxylation. However, addition of Sc 3+ activates the 1/H 2 O 2 reaction mixture to be able to hydroxylate cyclohexane and benzene within seconds at -40 °C. A metastable S = 1/2 Fe III -(η 1 -OOH) intermediate 2 is trapped at -40 °C, which undergoes rapid decay upon addition of Sc 3+ at rates independent of [substrate] but linearly dependent on [Sc 3+ ]. HClO 4 elicits comparable reactivity as Sc 3+ at the same concentration. We thus postulate that these additives both facilitate O-O bond heterolysis of 2 to form a common highly electrophilic Fe V O oxidant that is comparably reactive to the fastest nonheme high-valent iron-oxo oxidants found to date.

Original languageEnglish (US)
Pages (from-to)5798-5804
Number of pages7
JournalJournal of the American Chemical Society
Volume140
Issue number17
DOIs
StatePublished - May 2 2018

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Hydroxylation
Cyclohexane
Benzene
Oxidants
Chemical activation
Hexanes
Hexane
Iron
Oxidation
Catalysts
Substrates

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural

Cite this

Sc 3+ (or HClO 4 ) Activation of a Nonheme Fe III -OOH Intermediate for the Rapid Hydroxylation of Cyclohexane and Benzene . / Kal, Subhasree; Draksharapu, Apparao; Que, Larry.

In: Journal of the American Chemical Society, Vol. 140, No. 17, 02.05.2018, p. 5798-5804.

Research output: Contribution to journalArticle

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abstract = "[Fe(β-BPMCN)(CH 3 CN) 2 ] 2+ (1, BPMCN = N,N′-bis(pyridyl-2-methyl)-N,N′-dimethyl-trans-1,2-diaminocyclo-hexane) is a relatively poor catalyst for cyclohexane oxidation by H 2 O 2 and cannot perform benzene hydroxylation. However, addition of Sc 3+ activates the 1/H 2 O 2 reaction mixture to be able to hydroxylate cyclohexane and benzene within seconds at -40 °C. A metastable S = 1/2 Fe III -(η 1 -OOH) intermediate 2 is trapped at -40 °C, which undergoes rapid decay upon addition of Sc 3+ at rates independent of [substrate] but linearly dependent on [Sc 3+ ]. HClO 4 elicits comparable reactivity as Sc 3+ at the same concentration. We thus postulate that these additives both facilitate O-O bond heterolysis of 2 to form a common highly electrophilic Fe V O oxidant that is comparably reactive to the fastest nonheme high-valent iron-oxo oxidants found to date.",
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N2 - [Fe(β-BPMCN)(CH 3 CN) 2 ] 2+ (1, BPMCN = N,N′-bis(pyridyl-2-methyl)-N,N′-dimethyl-trans-1,2-diaminocyclo-hexane) is a relatively poor catalyst for cyclohexane oxidation by H 2 O 2 and cannot perform benzene hydroxylation. However, addition of Sc 3+ activates the 1/H 2 O 2 reaction mixture to be able to hydroxylate cyclohexane and benzene within seconds at -40 °C. A metastable S = 1/2 Fe III -(η 1 -OOH) intermediate 2 is trapped at -40 °C, which undergoes rapid decay upon addition of Sc 3+ at rates independent of [substrate] but linearly dependent on [Sc 3+ ]. HClO 4 elicits comparable reactivity as Sc 3+ at the same concentration. We thus postulate that these additives both facilitate O-O bond heterolysis of 2 to form a common highly electrophilic Fe V O oxidant that is comparably reactive to the fastest nonheme high-valent iron-oxo oxidants found to date.

AB - [Fe(β-BPMCN)(CH 3 CN) 2 ] 2+ (1, BPMCN = N,N′-bis(pyridyl-2-methyl)-N,N′-dimethyl-trans-1,2-diaminocyclo-hexane) is a relatively poor catalyst for cyclohexane oxidation by H 2 O 2 and cannot perform benzene hydroxylation. However, addition of Sc 3+ activates the 1/H 2 O 2 reaction mixture to be able to hydroxylate cyclohexane and benzene within seconds at -40 °C. A metastable S = 1/2 Fe III -(η 1 -OOH) intermediate 2 is trapped at -40 °C, which undergoes rapid decay upon addition of Sc 3+ at rates independent of [substrate] but linearly dependent on [Sc 3+ ]. HClO 4 elicits comparable reactivity as Sc 3+ at the same concentration. We thus postulate that these additives both facilitate O-O bond heterolysis of 2 to form a common highly electrophilic Fe V O oxidant that is comparably reactive to the fastest nonheme high-valent iron-oxo oxidants found to date.

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