Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate

Feifei Li; Katherine M. Van Heuvelen; Katlyn K. Meier; Eckard Münck; Lawrence Que

doi:10.1021/ja402645y

Sc³⁺-triggered oxoiron(IV) formation from O₂ and its non-heme iron(II) precursor via a Sc³⁺-peroxo-Fe³⁺ intermediate

Feifei Li
, Katherine M. Van Heuvelen
, Katlyn K. Meier
, Eckard Münck
, Lawrence Que

Chemistry (Twin Cities)

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

95 Scopus citations

Abstract

We report that redox-inactive Sc³⁺ can trigger O₂ activation by the Fe^II(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh ₄^- as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc³⁺ adduct of [Fe^III(η²-O₂)(TMC)]⁺ by an alternative route, which was found to have an Fe³⁺-(μ- η²:η²-peroxo)-Sc³⁺ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O₂ activation at non-heme iron centers.

Original language	English (US)
Pages (from-to)	10198-10201
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	135
Issue number	28
DOIs	https://doi.org/10.1021/ja402645y
State	Published - Jul 17 2013

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Copyright 2013 Elsevier B.V., All rights reserved.

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10.1021/ja402645y

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title = "Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate",

abstract = "We report that redox-inactive Sc3+ can trigger O2 activation by the FeII(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh 4- as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc3+ adduct of [FeIII(η2-O2)(TMC)]+ by an alternative route, which was found to have an Fe3+-(μ- η2:η2-peroxo)-Sc3+ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O2 activation at non-heme iron centers.",

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T1 - Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate

AU - Li, Feifei

AU - Van Heuvelen, Katherine M.

AU - Meier, Katlyn K.

AU - Münck, Eckard

AU - Que, Lawrence

PY - 2013/7/17

Y1 - 2013/7/17

N2 - We report that redox-inactive Sc3+ can trigger O2 activation by the FeII(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh 4- as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc3+ adduct of [FeIII(η2-O2)(TMC)]+ by an alternative route, which was found to have an Fe3+-(μ- η2:η2-peroxo)-Sc3+ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O2 activation at non-heme iron centers.

AB - We report that redox-inactive Sc3+ can trigger O2 activation by the FeII(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh 4- as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc3+ adduct of [FeIII(η2-O2)(TMC)]+ by an alternative route, which was found to have an Fe3+-(μ- η2:η2-peroxo)-Sc3+ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O2 activation at non-heme iron centers.

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