Designing ligands to achieve robust oxidation catalysts. Iron based systems

Michael J. Bartos; Scott W. Gordon-Wylie; Brian G. Fox; L. James Wright; Susan T. Weintraub; Karl E. Kauffmann; Eckard Münck; Kimberly L. Kostka; Erich S. Uffelman; Clifton E.F. Rickard; Kathleen R. Noon; Terrence J. Collins

doi:10.1016/S0010-8545(98)00142-8

Designing ligands to achieve robust oxidation catalysts. Iron based systems

Michael J. Bartos
, Scott W. Gordon-Wylie
, Brian G. Fox
, L. James Wright
, Susan T. Weintraub
, Karl E. Kauffmann
, Eckard Münck
, Kimberly L. Kostka
, Erich S. Uffelman
, Clifton E.F. Rickard
, Kathleen R. Noon
, Terrence J. Collins

Department of Biochemistry & Structural Biology

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

73 Scopus citations

Abstract

Nitrile solvents containing α-CH substituents are catalytically oxidized by the tetraamido-N-Fe^III-aqua complex, 3, with t-butyl hydroperoxide. Every observable product resulting from 3 has been characterized. An Fe^IV-cyano complex, 5, is the major inorganic product; the cyano ligand emanates from the solvent-substrate. A new type of ligand oxidative degradation giving 6 proceeds to ca. 10% of the iron macrocycle; its characterization indicates how the already robust macrocycle should be redesigned to further improve its oxidative stability. Such improvement has led to long-lived catalysts for hydrogen peroxide oxidation in water from neutral to basic pH at room temperature.

Original language	English (US)
Pages (from-to)	361-390
Number of pages	30
Journal	Coordination Chemistry Reviews
Volume	174
Issue number	1
DOIs	https://doi.org/10.1016/S0010-8545(98)00142-8
State	Published - Jul 1998

Keywords

High valent iron complexes
Iron-57 Mössbauer spectroscopy
Ligand design
Ligand oxidative degradation

ASJC Scopus subject areas

General Chemistry
Materials Chemistry
Inorganic Chemistry
Physical and Theoretical Chemistry

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10.1016/S0010-8545(98)00142-8

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Bartos, M. J., Gordon-Wylie, S. W., Fox, B. G., Wright, L. J., Weintraub, S. T., Kauffmann, K. E., Münck, E., Kostka, K. L., Uffelman, E. S., Rickard, C. E. F., Noon, K. R., & Collins, T. J. (1998). Designing ligands to achieve robust oxidation catalysts. Iron based systems. Coordination Chemistry Reviews, 174(1), 361-390. https://doi.org/10.1016/S0010-8545(98)00142-8

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title = "Designing ligands to achieve robust oxidation catalysts. Iron based systems",

abstract = "Nitrile solvents containing α-CH substituents are catalytically oxidized by the tetraamido-N-FeIII-aqua complex, 3, with t-butyl hydroperoxide. Every observable product resulting from 3 has been characterized. An FeIV-cyano complex, 5, is the major inorganic product; the cyano ligand emanates from the solvent-substrate. A new type of ligand oxidative degradation giving 6 proceeds to ca. 10\% of the iron macrocycle; its characterization indicates how the already robust macrocycle should be redesigned to further improve its oxidative stability. Such improvement has led to long-lived catalysts for hydrogen peroxide oxidation in water from neutral to basic pH at room temperature.",

keywords = "High valent iron complexes, Iron-57 M{\"o}ssbauer spectroscopy, Ligand design, Ligand oxidative degradation",

author = "Bartos, \{Michael J.\} and Gordon-Wylie, \{Scott W.\} and Fox, \{Brian G.\} and Wright, \{L. James\} and Weintraub, \{Susan T.\} and Kauffmann, \{Karl E.\} and Eckard M{\"u}nck and Kostka, \{Kimberly L.\} and Uffelman, \{Erich S.\} and Rickard, \{Clifton E.F.\} and Noon, \{Kathleen R.\} and Collins, \{Terrence J.\}",

note = "Funding Information: This work was supported by the NIH, GM44867 (T.J.C.) and GM22701 (E.M.). We thank Professor Larry Que and Dr Anne True of the University of Minnesota for EXAFS analysis of 5 and Professor David Bocian for ascertaining that 5 rapidly photobleaches when studied by resonance Raman. We also thank Dr Colin Horwitz of Carnegie Mellon University for helpful discussions. ",

year = "1998",

month = jul,

doi = "10.1016/S0010-8545(98)00142-8",

language = "English (US)",

volume = "174",

pages = "361--390",

journal = "Coordination Chemistry Reviews",

issn = "0010-8545",

publisher = "Elsevier B.V.",

number = "1",

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TY - JOUR

T1 - Designing ligands to achieve robust oxidation catalysts. Iron based systems

AU - Bartos, Michael J.

AU - Gordon-Wylie, Scott W.

AU - Fox, Brian G.

AU - Wright, L. James

AU - Weintraub, Susan T.

AU - Kauffmann, Karl E.

AU - Münck, Eckard

AU - Kostka, Kimberly L.

AU - Uffelman, Erich S.

AU - Rickard, Clifton E.F.

AU - Noon, Kathleen R.

AU - Collins, Terrence J.

N1 - Funding Information: This work was supported by the NIH, GM44867 (T.J.C.) and GM22701 (E.M.). We thank Professor Larry Que and Dr Anne True of the University of Minnesota for EXAFS analysis of 5 and Professor David Bocian for ascertaining that 5 rapidly photobleaches when studied by resonance Raman. We also thank Dr Colin Horwitz of Carnegie Mellon University for helpful discussions.

PY - 1998/7

Y1 - 1998/7

N2 - Nitrile solvents containing α-CH substituents are catalytically oxidized by the tetraamido-N-FeIII-aqua complex, 3, with t-butyl hydroperoxide. Every observable product resulting from 3 has been characterized. An FeIV-cyano complex, 5, is the major inorganic product; the cyano ligand emanates from the solvent-substrate. A new type of ligand oxidative degradation giving 6 proceeds to ca. 10% of the iron macrocycle; its characterization indicates how the already robust macrocycle should be redesigned to further improve its oxidative stability. Such improvement has led to long-lived catalysts for hydrogen peroxide oxidation in water from neutral to basic pH at room temperature.

AB - Nitrile solvents containing α-CH substituents are catalytically oxidized by the tetraamido-N-FeIII-aqua complex, 3, with t-butyl hydroperoxide. Every observable product resulting from 3 has been characterized. An FeIV-cyano complex, 5, is the major inorganic product; the cyano ligand emanates from the solvent-substrate. A new type of ligand oxidative degradation giving 6 proceeds to ca. 10% of the iron macrocycle; its characterization indicates how the already robust macrocycle should be redesigned to further improve its oxidative stability. Such improvement has led to long-lived catalysts for hydrogen peroxide oxidation in water from neutral to basic pH at room temperature.

KW - High valent iron complexes

KW - Iron-57 Mössbauer spectroscopy

KW - Ligand design

KW - Ligand oxidative degradation

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DO - 10.1016/S0010-8545(98)00142-8

M3 - Article

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SN - 0010-8545

VL - 174

SP - 361

EP - 390

JO - Coordination Chemistry Reviews

JF - Coordination Chemistry Reviews

IS - 1

ER -

Designing ligands to achieve robust oxidation catalysts. Iron based systems

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Keywords

ASJC Scopus subject areas

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