A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol

Juan Chen; Stepan Stepanovic; Apparao Draksharapu; Maja Gruden; Wesley R. Browne

doi:10.1002/anie.201712678

A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol

Juan Chen, Stepan Stepanovic, Apparao Draksharapu, Maja Gruden, Wesley R. Browne

Chemistry (Twin Cities)

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

30 Scopus citations

Abstract

Non-heme (L)Fe^III and (L)Fe^III-O-Fe^III(L) complexes (L=1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) underwent reduction under irradiation to the Fe^II state with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT studies support a mechanism in which irradiation results in charge-transfer excitation of a Fe^III−μ-O−Fe^III complex to generate [(L)Fe^IV=O]²⁺ (observed transiently during irradiation in acetonitrile), and an equivalent of (L)Fe^II. Under aerobic conditions, irradiation accelerates reoxidation from the Fe^II to the Fe^III state with O₂, thus closing the cycle of methanol oxidation to methanal.

Original language	English (US)
Pages (from-to)	3207-3211
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	12
DOIs	https://doi.org/10.1002/anie.201712678
State	Published - Mar 12 2018

Bibliographical note

Publisher Copyright:
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Keywords

diiron complexes
iron
oxidation
photochemistry
reaction mechanisms

Access

10.1002/anie.201712678

OpenUrl availability

Full text

Cite this

@article{429d9fe4565f4344bdc7d3aec56f2fc0,

title = "A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol",

abstract = "Non-heme (L)FeIII and (L)FeIII-O-FeIII(L) complexes (L=1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) underwent reduction under irradiation to the FeII state with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT studies support a mechanism in which irradiation results in charge-transfer excitation of a FeIII−μ-O−FeIII complex to generate [(L)FeIV=O]2+ (observed transiently during irradiation in acetonitrile), and an equivalent of (L)FeII. Under aerobic conditions, irradiation accelerates reoxidation from the FeII to the FeIII state with O2, thus closing the cycle of methanol oxidation to methanal.",

keywords = "diiron complexes, iron, oxidation, photochemistry, reaction mechanisms",

author = "Juan Chen and Stepan Stepanovic and Apparao Draksharapu and Maja Gruden and Browne, {Wesley R.}",

note = "Publisher Copyright: {\textcopyright} 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.",

year = "2018",

month = mar,

day = "12",

doi = "10.1002/anie.201712678",

language = "English (US)",

volume = "57",

pages = "3207--3211",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "12",

}

TY - JOUR

T1 - A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol

AU - Chen, Juan

AU - Stepanovic, Stepan

AU - Draksharapu, Apparao

AU - Gruden, Maja

AU - Browne, Wesley R.

PY - 2018/3/12

Y1 - 2018/3/12

N2 - Non-heme (L)FeIII and (L)FeIII-O-FeIII(L) complexes (L=1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) underwent reduction under irradiation to the FeII state with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT studies support a mechanism in which irradiation results in charge-transfer excitation of a FeIII−μ-O−FeIII complex to generate [(L)FeIV=O]2+ (observed transiently during irradiation in acetonitrile), and an equivalent of (L)FeII. Under aerobic conditions, irradiation accelerates reoxidation from the FeII to the FeIII state with O2, thus closing the cycle of methanol oxidation to methanal.

AB - Non-heme (L)FeIII and (L)FeIII-O-FeIII(L) complexes (L=1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine) underwent reduction under irradiation to the FeII state with concomitant oxidation of methanol to methanal, without the need for a secondary photosensitizer. Spectroscopic and DFT studies support a mechanism in which irradiation results in charge-transfer excitation of a FeIII−μ-O−FeIII complex to generate [(L)FeIV=O]2+ (observed transiently during irradiation in acetonitrile), and an equivalent of (L)FeII. Under aerobic conditions, irradiation accelerates reoxidation from the FeII to the FeIII state with O2, thus closing the cycle of methanol oxidation to methanal.

KW - diiron complexes

KW - iron

KW - oxidation

KW - photochemistry

KW - reaction mechanisms

UR - http://www.scopus.com/inward/record.url?scp=85042067927&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042067927&partnerID=8YFLogxK

U2 - 10.1002/anie.201712678

DO - 10.1002/anie.201712678

M3 - Article

C2 - 29334586

AN - SCOPUS:85042067927

SN - 1433-7851

VL - 57

SP - 3207

EP - 3211

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 12

ER -

A Non-Heme Iron Photocatalyst for Light-Driven Aerobic Oxidation of Methanol

Abstract

Bibliographical note

Keywords

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this