Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation

Moore, Jewelianna M.; Park, Yun Ji; Fout, Alison R.

doi:10.1021/acs.organomet.4c00454

Title: Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation

Journal Article · 16 January 2025 · Organometallics

DOI: https://doi.org/10.1021/acs.organomet.4c00454 · OSTI ID:2513947

Moore, Jewelianna M. ^[1]; Park, Yun Ji ^[2];

^[1]

Texas A&M University, College Station, TX (United States)
University of Illinois at Urbana−Champaign, IL (United States)

High-valent iron complexes play a crucial role in the oxidation of organic substrates, especially in C–H bond functionalization reactions in biology. This paper investigates the reactivity of nonporphyrin tripodal ligands featuring a secondary coordination sphere, focusing on their prospective ability to stabilize high-valent iron-oxo species. Using NMR spectroscopy and X-ray crystallography, we detail the formation of an Fe(III)-alkoxide complex through intramolecular C–H bond activation, providing insight into the potential transient formation of a high-valent iron-oxo intermediate. While attempts to observe an Fe(IV)-oxo complex were unsuccessful, our findings underscore the significance of the ligand electronic environment in stabilizing reactive iron species for C–H bond activation.

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Research Organization:: Texas A&M University, College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0025026

OSTI ID:: 2513947

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 3 Vol. 44; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

A Synthetic High-Spin Oxoiron(IV) Complex: Generation, Spectroscopic Characterization, and Reactivity England, Jason; Martinho, Marlène; Farquhar, Erik R. Angewandte Chemie International Edition, Vol. 48, Issue 20 https://doi.org/10.1002/anie.200900863	journal	May 2009
Mononuclear Nonheme Iron(III)-Iodosylarene and High-Valent Iron-Oxo Complexes in Olefin Epoxidation Reactions Wang, Bin; Lee, Yong-Min; Seo, Mi Sook Angewandte Chemie International Edition, Vol. 54, Issue 40 https://doi.org/10.1002/anie.201505796	journal	August 2015
Modeling the cis-Oxo-Labile Binding Site Motif of Non-Heme Iron Oxygenases: Water Exchange and Oxidation Reactivity of a Non-Heme Iron(IV)-Oxo Compound Bearing a Tripodal Tetradentate Ligand Company, Anna; Prat, Irene; Frisch, Jonathan R. Chemistry - A European Journal, Vol. 17, Issue 5 https://doi.org/10.1002/chem.201002297	journal	January 2011
Theoretical Identification of the Factors Governing the Reactivity of C−H Bond Activation by Non‐Heme Iron(IV)‐Oxo Complexes Roy, Lisa ChemPlusChem, Vol. 84, Issue 7 https://doi.org/10.1002/cplu.201900178	journal	June 2019
The mystery of cytochrome P450 Compound I Jung, Christiane Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics, Vol. 1814, Issue 1 https://doi.org/10.1016/j.bbapap.2010.06.007	journal	January 2011
Enzymatic C–H activation by metal–superoxo intermediates Bollinger, J. Martin; Krebs, Carsten Current Opinion in Chemical Biology, Vol. 11, Issue 2 https://doi.org/10.1016/j.cbpa.2007.02.037	journal	April 2007
High-valent iron in chemical and biological oxidations Groves, John T. Journal of Inorganic Biochemistry, Vol. 100, Issue 4 https://doi.org/10.1016/j.jinorgbio.2006.01.012	journal	April 2006
The Fe(PDP)-catalyzed aliphatic C–H oxidation: a slow addition protocol Vermeulen, Nicolaas A.; Chen, Mark S.; Christina White, M. Tetrahedron, Vol. 65, Issue 16 https://doi.org/10.1016/j.tet.2008.11.082	journal	April 2009
C–H Bond Cleavage by Bioinspired Nonheme Metal Complexes Lee, Justin L.; Ross, Dolores L.; Barman, Suman K. Inorganic Chemistry, Vol. 60, Issue 18 https://doi.org/10.1021/acs.inorgchem.1c01754	journal	September 2021
Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study Park, Yun Ji; Peñas-Defrutos, Marconi N.; Drummond, Michael J. Inorganic Chemistry, Vol. 61, Issue 21 https://doi.org/10.1021/acs.inorgchem.2c00462	journal	May 2022
Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)–Hydroxo Complexes through Primary and Secondary Coordination Sphere Modifications Gordon, Zachary; Drummond, Michael J.; Matson, Ellen M. Inorganic Chemistry, Vol. 56, Issue 9 https://doi.org/10.1021/acs.inorgchem.6b03071	journal	April 2017
Characterization of Terminal Iron(III)–Oxo and Iron(III)–Hydroxo Complexes Derived from O ₂ Activation Gordon, Zachary; Miller, Tabitha J.; Leahy, Clare A. Inorganic Chemistry, Vol. 58, Issue 23 https://doi.org/10.1021/acs.inorgchem.9b02079	journal	November 2019
Mechanisms of Cytochrome P450-Catalyzed Oxidations Guengerich, F. Peter ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b03401	journal	October 2018
Catalytic Perchlorate Reduction Using Iron: Mechanistic Insights and Improved Catalyst Turnover Drummond, Michael J.; Miller, Tabitha J.; Ford, Courtney L. ACS Catalysis, Vol. 10, Issue 5 https://doi.org/10.1021/acscatal.9b05029	journal	February 2020
Bioinspired Hydrogen Bond Motifs in Ligand Design: The Role of Noncovalent Interactions in Metal Ion Mediated Activation of Dioxygen Borovik, A. S. Accounts of Chemical Research, Vol. 38, Issue 1 https://doi.org/10.1021/ar030160q	journal	January 2005
The Road to Non-Heme Oxoferryls and Beyond ^† Que, Lawrence Accounts of Chemical Research, Vol. 40, Issue 7 https://doi.org/10.1021/ar700024g	journal	July 2007
High-Valent Iron(IV)–Oxo Complexes of Heme and Non-Heme Ligands in Oxygenation Reactions Nam, Wonwoo Accounts of Chemical Research, Vol. 40, Issue 7 https://doi.org/10.1021/ar700027f	journal	July 2007
Structure and Chemistry of Cytochrome P450 Denisov, Ilia G.; Makris, Thomas M.; Sligar, Stephen G. Chemical Reviews, Vol. 105, Issue 6 https://doi.org/10.1021/cr0307143	journal	June 2005
C−H Bond Activations by Metal Oxo Compounds Gunay, Ahmet; Theopold, Klaus H. Chemical Reviews, Vol. 110, Issue 2 https://doi.org/10.1021/cr900269x	journal	February 2010
Isolation of Iron(II) Aqua and Hydroxyl Complexes Featuring a Tripodal H-bond Donor and Acceptor Ligand Matson, Ellen M.; Bertke, Jeffrey A.; Fout, Alison R. Inorganic Chemistry, Vol. 53, Issue 9 https://doi.org/10.1021/ic500102c	journal	April 2014
A Hydrogen-Bond Facilitated Cycle for Oxygen Reduction by an Acid- and Base-Compatible Iron Platform Soo, Han Sen; Komor, Alexis C.; Iavarone, Anthony T. Inorganic Chemistry, Vol. 48, Issue 21 https://doi.org/10.1021/ic9006668	journal	November 2009
Biomimetic Alkane Hydroxylations by an Iron(III) Porphyrin Complex with H ₂ O ₂ and by a High-Valent Iron(IV) Oxo Porphyrin Cation Radical Complex Nam, Wonwoo; Goh, Yeong Mee; Lee, Yoon Jung Inorganic Chemistry, Vol. 38, Issue 13 https://doi.org/10.1021/ic980670u	journal	June 1999
Reactive iron porphyrin derivatives related to the catalytic cycles of cytochrome P-450 and peroxidase. Studies of the mechanism of oxygen activation Groves, John T.; Watanabe, Yoshihito. Journal of the American Chemical Society, Vol. 110, Issue 25 https://doi.org/10.1021/ja00233a021	journal	December 1988
High-valent iron-porphyrin complexes related to peroxidase and cytochrome P-450 Groves, John T.; Haushalter, Robert C.; Nakamura, Mikio Journal of the American Chemical Society, Vol. 103, Issue 10 https://doi.org/10.1021/ja00400a075	journal	May 1981
Hydroxylation and epoxidation catalyzed by iron-porphine complexes. Oxygen transfer from iodosylbenzene Groves, John T.; Nemo, Thomas E.; Myers, Richard S. Journal of the American Chemical Society, Vol. 101, Issue 4 https://doi.org/10.1021/ja00498a040	journal	February 1979
N ₂ O Activation and Oxidation Reactivity from a Non-Heme Iron Pyrrole Platform Harman, W. Hill; Chang, Christopher J. Journal of the American Chemical Society, Vol. 129, Issue 49 https://doi.org/10.1021/ja076842g	journal	December 2007
The Crystal Structure of a High-Spin Oxoiron(IV) Complex and Characterization of Its Self-Decay Pathway England, Jason; Guo, Yisong; Farquhar, Erik R. Journal of the American Chemical Society, Vol. 132, Issue 25 https://doi.org/10.1021/ja100366c	journal	June 2010
Formation, Structure, and EPR Detection of a High Spin Fe ^IV —Oxo Species Derived from Either an Fe ^III —Oxo or Fe ^III —OH Complex Lacy, David C.; Gupta, Rupal; Stone, Kari L. Journal of the American Chemical Society, Vol. 132, Issue 35 https://doi.org/10.1021/ja1047818	journal	September 2010
A More Reactive Trigonal-Bipyramidal High-Spin Oxoiron(IV) Complex with a cis-Labile Site England, Jason; Guo, Yisong; Van Heuvelen, Katherine M. Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja2040909	journal	August 2011
A High-Spin Iron(IV)–Oxo Complex Supported by a Trigonal Nonheme Pyrrolide Platform Bigi, Julian P.; Harman, W. Hill; Lassalle-Kaiser, Benedikt Journal of the American Chemical Society, Vol. 134, Issue 3 https://doi.org/10.1021/ja207048h	journal	January 2012
Directed Metal (Oxo) Aliphatic C–H Hydroxylations: Overriding Substrate Bias Bigi, Marinus A.; Reed, Sean A.; White, M. Christina Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja301685r	journal	May 2012
Electron Paramagnetic Resonance and Mössbauer Spectroscopy and Density Functional Theory Analysis of a High-Spin Fe ^IV –Oxo Complex Gupta, Rupal; Lacy, David C.; Bominaar, Emile L. Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja303224p	journal	May 2012
Facile Nitrite Reduction in a Non-heme Iron System: Formation of an Iron(III)-Oxo Matson, Ellen M.; Park, Yun Ji; Fout, Alison R. Journal of the American Chemical Society, Vol. 136, Issue 50 https://doi.org/10.1021/ja510615p	journal	December 2014
Modeling TauD- J : A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C–H Bonds Biswas, Achintesh N.; Puri, Mayank; Meier, Katlyn K. Journal of the American Chemical Society, Vol. 137, Issue 7 https://doi.org/10.1021/ja511757j	journal	February 2015
Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes Oswald, Victoria F.; Lee, Justin L.; Biswas, Saborni Journal of the American Chemical Society, Vol. 142, Issue 27 https://doi.org/10.1021/jacs.0c03085	journal	June 2020
Formation of Red Elemental Selenium from Seleniferous Oxyanions: Deoxygenation by a Homogeneous Iron Catalyst Gullett, Kelly L.; Ford, Courtney L.; Garvey, Ian J. Journal of the American Chemical Society, Vol. 145, Issue 38 https://doi.org/10.1021/jacs.3c05981	journal	September 2023
Reactivity of an Fe ^IV -Oxo Complex with Protons and Oxidants Hill, Ethan A.; Weitz, Andrew C.; Onderko, Elizabeth Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b07633	journal	September 2016
C–H activation Bergman, Robert G. Nature, Vol. 446, Issue 7134 https://doi.org/10.1038/446391a	journal	March 2007
Diverting non-haem iron catalysed aliphatic C–H hydroxylations towards desaturations Bigi, Marinus A.; Reed, Sean A.; White, M. Christina Nature Chemistry, Vol. 3, Issue 3 https://doi.org/10.1038/nchem.967	journal	January 2011
Nonheme oxoiron( iv ) complexes of pentadentate N5 ligands: spectroscopy, electrochemistry, and oxidative reactivity Wang, Dong; Ray, Kallol; Collins, Michael J. Chem. Sci., Vol. 4, Issue 1 https://doi.org/10.1039/C2SC21318D	journal	January 2013
Synthesis and characterization of tetrapodal nickel complexes with adaptable ligand binding geometries Cho, Hsien-Liang; Gullett, Kelly L.; Fout, Alison R. Chemical Communications, Vol. 60, Issue 76 https://doi.org/10.1039/D4CC03186E	journal	January 2024
Role of metal–oxo complexes in the cleavage of C–H bonds Borovik, A. S. Chemical Society Reviews, Vol. 40, Issue 4 https://doi.org/10.1039/c0cs00165a	journal	January 2011
Donor-extended tripodal pyrroles: encapsulation, metallation, and H-bonded tautomers Hart, John S.; White, Fraser J.; Love, Jason B. Chemical Communications, Vol. 47, Issue 20 https://doi.org/10.1039/c1cc11378j	journal	January 2011
A mononuclear nonheme iron(iv)-oxo complex which is more reactive than cytochrome P450 model compound I Seo, Mi Sook; Kim, Nam Hee; Cho, Kyung-Bin Chemical Science, Vol. 2, Issue 6 https://doi.org/10.1039/c1sc00062d	journal	January 2011
Structure and function of the cytochrome P450 peroxygenase enzymes Munro, Andrew W.; McLean, Kirsty J.; Grant, Job L. Biochemical Society Transactions, Vol. 46, Issue 1 https://doi.org/10.1042/BST20170218	journal	February 2018
Cafestol to Tricalysiolide B and Oxidized Analogues: Biosynthetic and Derivatization Studies Using Non-heme Iron Catalyst Fe(PDP) Houk, K.; White, M.; Bigi, Marinus Synlett, Vol. 23, Issue 19 https://doi.org/10.1055/s-0032-1317708	journal	November 2012
Varying the secondary coordination sphere: synthesis of cobalt and iron complexes of a tripodal ligand featuring two hydrogen-bond donors or acceptors Ford, Courtney L.; Miller, Tabitha J.; Park, Yun Ji Journal of Coordination Chemistry, Vol. 73, Issue 15 https://doi.org/10.1080/00958972.2020.1822523	journal	August 2020
A Predictably Selective Aliphatic C H Oxidation Reaction for Complex Molecule Synthesis Chen, M. S.; White, M. C. Science, Vol. 318, Issue 5851 https://doi.org/10.1126/science.1148597	journal	November 2007
Combined Effects on Selectivity in Fe-Catalyzed Methylene Oxidation Chen, M. S.; White, M. C. Science, Vol. 327, Issue 5965 https://doi.org/10.1126/science.1183602	journal	January 2010
O2 Activation by Nonheme Iron Complexes: A Monomeric Fe(III)-Oxo Complex Derived From O2 MacBeth, C. E. Science, Vol. 289, Issue 5481 https://doi.org/10.1126/science.289.5481.938	journal	August 2000
A bioinspired iron catalyst for nitrate and perchlorate reduction Ford, Courtney L.; Park, Yun Ji; Matson, Ellen M. Science, Vol. 354, Issue 6313 https://doi.org/10.1126/science.aah6886	journal	November 2016

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Iron
Iron complexes
Ligands
Nuclear magnetic resonance spectroscopy
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Title: Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation

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