2H1C Mimicry: Bioinspired Iron and Zinc Complexes Supported by
              N,N,O
              Phenolate Ligands

Emily C. Monkcom; Hidde A. Negenman; Eduard Masferrer‐rius; Martin Lutz; Shengfa Ye; Eckhard Bill; Robertus J. M. Klein Gebbink

doi:10.1002/ejic.202101046

2H1C Mimicry: Bioinspired Iron and Zinc Complexes Supported by N,N,O Phenolate Ligands

Emily C. Monkcom
, Hidde A. Negenman
, Eduard Masferrer‐rius
, Martin Lutz
, Shengfa Ye
, Eckhard Bill
, Robertus J. M. Klein Gebbink

Utrecht University
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences 457 Zhongshan Road Dalian 116023 China
Max-Planck-Institut für Chemische Energiekonversion Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr Germany

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

Abstract

In pursuit of mimicking the ubiquitous 2H1C motif in mononuclear non-heme iron enzymes, two new bioinspired N,N,O phenolate ligands, BenzImNNO and Im^Ph2NNO, are synthesised and their coordination chemistry with zinc(II) and iron(II) is explored. BenzImNNO coordinates by means of an anionic κ₃-N,N,O donor set and readily forms homoleptic bisligated complexes, also in the presence of equimolar amounts of metal salt. In contrast, the increased steric bulk of Im^Ph2NNO promotes the formation of dinuclear complexes, [M₂(Im^Ph2NNO)₂(OTf)₂] (M=Fe, Zn), with facially opposing metal sites, as a result of its unique bridging μ₂:κ₂-N,N:κ₁-O coordination mode. We investigate the robustness of the ligand's dinucleating coordination mode during oxidative transformations and demonstrate that its coordination mode is retained upon triflate substitution for a biorelevant thiophenolate co-ligand.

Original language	English
Article number	e202101046
Pages (from-to)	1-14
Journal	Berichte der deutschen chemischen Gesellschaft
Volume	2022
Issue number	9
DOIs	https://doi.org/10.1002/ejic.202101046
Publication status	Published - 29 Mar 2022

Bibliographical note

Funding Information:
This work was financially supported by the European Union under the Marie Sklodowska‐Curie NoNoMeCat ITN network grant agreement (675020‐MSCA‐ITN‐2015‐ETN). The X‐ray diffractometer was financed by the Netherlands Organisation for Scientific Research (NWO). This work was sponsored by NWO Exacte en Natuurwetenschappen (Physical Sciences) for the use of supercomputer facilities. We also wish to thank Bernd Mienert and Andreas Göbels (MPI) for their technical assistance with the Mössbauer and SQUID measurements. We kindly thank our colleagues Dr. Johann Jastrzebski, Dr. Léon Witteman and Serhii Tretiakov at Utrecht University for their assistance and helpful discussions regarding the NMR experiments.

Publisher Copyright:
© 2022 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.

Keywords

Bioinorganic chemistry
Enzyme models
IPNS
Iron
N,N,O ligands

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10.1002/ejic.202101046Licence: CC BY-NC

Eur J Inorg Chem - 2022 - Monkcom - 2H1C Mimicry Bioinspired Iron and Zinc Complexes Supported by N N O Phenolate LigandsFinal published version, 7.07 MBLicence: CC BY-NC

https://onlinelibrary.wiley.com/doi/10.1002/ejic.202101046

Cite this

@article{a91f777b8edb47acaf578fea42f80dd9,

title = "2H1C Mimicry: Bioinspired Iron and Zinc Complexes Supported by N,N,O Phenolate Ligands",

abstract = "In pursuit of mimicking the ubiquitous 2H1C motif in mononuclear non-heme iron enzymes, two new bioinspired N,N,O phenolate ligands, BenzImNNO and ImPh2NNO, are synthesised and their coordination chemistry with zinc(II) and iron(II) is explored. BenzImNNO coordinates by means of an anionic κ3-N,N,O donor set and readily forms homoleptic bisligated complexes, also in the presence of equimolar amounts of metal salt. In contrast, the increased steric bulk of ImPh2NNO promotes the formation of dinuclear complexes, [M2(ImPh2NNO)2(OTf)2] (M=Fe, Zn), with facially opposing metal sites, as a result of its unique bridging μ2:κ2-N,N:κ1-O coordination mode. We investigate the robustness of the ligand's dinucleating coordination mode during oxidative transformations and demonstrate that its coordination mode is retained upon triflate substitution for a biorelevant thiophenolate co-ligand.",

keywords = "Bioinorganic chemistry, Enzyme models, IPNS, Iron, N,N,O ligands",

author = "Monkcom, \{Emily C.\} and Negenman, \{Hidde A.\} and Eduard Masferrer‐rius and Martin Lutz and Shengfa Ye and Eckhard Bill and \{Klein Gebbink\}, \{Robertus J. M.\}",

note = "Funding Information: This work was financially supported by the European Union under the Marie Sklodowska‐Curie NoNoMeCat ITN network grant agreement (675020‐MSCA‐ITN‐2015‐ETN). The X‐ray diffractometer was financed by the Netherlands Organisation for Scientific Research (NWO). This work was sponsored by NWO Exacte en Natuurwetenschappen (Physical Sciences) for the use of supercomputer facilities. We also wish to thank Bernd Mienert and Andreas G{\"o}bels (MPI) for their technical assistance with the M{\"o}ssbauer and SQUID measurements. We kindly thank our colleagues Dr. Johann Jastrzebski, Dr. L{\'e}on Witteman and Serhii Tretiakov at Utrecht University for their assistance and helpful discussions regarding the NMR experiments. Publisher Copyright: {\textcopyright} 2022 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.",

year = "2022",

month = mar,

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doi = "10.1002/ejic.202101046",

language = "English",

volume = "2022",

pages = "1--14",

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2H1C Mimicry: Bioinspired Iron and Zinc Complexes Supported by N,N,O Phenolate Ligands. / Monkcom, Emily C.; Negenman, Hidde A.; Masferrer‐rius, Eduard et al.
In: Berichte der deutschen chemischen Gesellschaft, Vol. 2022, No. 9, e202101046, 29.03.2022, p. 1-14.

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

TY - JOUR

T1 - 2H1C Mimicry: Bioinspired Iron and Zinc Complexes Supported by N,N,O Phenolate Ligands

AU - Monkcom, Emily C.

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AU - Masferrer‐rius, Eduard

AU - Lutz, Martin

AU - Ye, Shengfa

AU - Bill, Eckhard

AU - Klein Gebbink, Robertus J. M.

N1 - Funding Information: This work was financially supported by the European Union under the Marie Sklodowska‐Curie NoNoMeCat ITN network grant agreement (675020‐MSCA‐ITN‐2015‐ETN). The X‐ray diffractometer was financed by the Netherlands Organisation for Scientific Research (NWO). This work was sponsored by NWO Exacte en Natuurwetenschappen (Physical Sciences) for the use of supercomputer facilities. We also wish to thank Bernd Mienert and Andreas Göbels (MPI) for their technical assistance with the Mössbauer and SQUID measurements. We kindly thank our colleagues Dr. Johann Jastrzebski, Dr. Léon Witteman and Serhii Tretiakov at Utrecht University for their assistance and helpful discussions regarding the NMR experiments. Publisher Copyright: © 2022 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.

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N2 - In pursuit of mimicking the ubiquitous 2H1C motif in mononuclear non-heme iron enzymes, two new bioinspired N,N,O phenolate ligands, BenzImNNO and ImPh2NNO, are synthesised and their coordination chemistry with zinc(II) and iron(II) is explored. BenzImNNO coordinates by means of an anionic κ3-N,N,O donor set and readily forms homoleptic bisligated complexes, also in the presence of equimolar amounts of metal salt. In contrast, the increased steric bulk of ImPh2NNO promotes the formation of dinuclear complexes, [M2(ImPh2NNO)2(OTf)2] (M=Fe, Zn), with facially opposing metal sites, as a result of its unique bridging μ2:κ2-N,N:κ1-O coordination mode. We investigate the robustness of the ligand's dinucleating coordination mode during oxidative transformations and demonstrate that its coordination mode is retained upon triflate substitution for a biorelevant thiophenolate co-ligand.

AB - In pursuit of mimicking the ubiquitous 2H1C motif in mononuclear non-heme iron enzymes, two new bioinspired N,N,O phenolate ligands, BenzImNNO and ImPh2NNO, are synthesised and their coordination chemistry with zinc(II) and iron(II) is explored. BenzImNNO coordinates by means of an anionic κ3-N,N,O donor set and readily forms homoleptic bisligated complexes, also in the presence of equimolar amounts of metal salt. In contrast, the increased steric bulk of ImPh2NNO promotes the formation of dinuclear complexes, [M2(ImPh2NNO)2(OTf)2] (M=Fe, Zn), with facially opposing metal sites, as a result of its unique bridging μ2:κ2-N,N:κ1-O coordination mode. We investigate the robustness of the ligand's dinucleating coordination mode during oxidative transformations and demonstrate that its coordination mode is retained upon triflate substitution for a biorelevant thiophenolate co-ligand.

KW - Bioinorganic chemistry

KW - Enzyme models

KW - IPNS

KW - Iron

KW - N,N,O ligands

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DO - 10.1002/ejic.202101046

M3 - Article

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