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

69 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

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials 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",

number = "1",

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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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Designing ligands to achieve robust oxidation catalysts. Iron based systems

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