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  Structurally Modelling the 2‐His‐1‐Carboxylate Facial Triad with a Bulky N,N,O Phenolate Ligand

Monkcom, E. C., de Bruin, D., de Vries, A. J., Lutz, M., Ye, S., & Klein Gebbink, R. J. M. (2021). Structurally Modelling the 2‐His‐1‐Carboxylate Facial Triad with a Bulky N,N,O Phenolate Ligand. Chemistry – A European Journal, 27(16), 5191-5204. doi:10.1002/chem.202004633.

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 Creators:
Monkcom, Emily C.1, Author
de Bruin, Daniël1, Author
de Vries, Annemiek J.1, Author
Lutz, Martin2, Author
Ye, Shengfa3, 4, Author              
Klein Gebbink, Robertus J. M.1, Author
Affiliations:
1Organic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands, ou_persistent22              
2Crystal and Structural Chemistry, Bijvoet Centre for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH, Utrecht, The Netherlands, ou_persistent22              
3State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023 P. R. China, ou_persistent22              
4Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

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Free keywords: 2-His-1-carboxylate facial triad; bioinspired; enzyme models; N,N,O ligand; non-heme iron
 Abstract: We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, ImPh2NNOtBu (L), designed to model the 2‐His‐1‐carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4‐di‐tert‐butyl‐subtituted phenolate. Reacting K‐L with MCl2 (M = Fe, Zn) affords the isostructural, tetrahedral non‐heme complexes [Fe(L)(Cl)] (1) and [Zn(L)(Cl)] (2) in high yield. The tridentate N,N,O ligand coordination observed in their X‐ray crystal structures remains intact and well‐defined in MeCN and CH2Cl2 solution. Reacting 2 with NaSPh affords a tetrahedral zinc thiolate complex, [Zn(L)(SPh)] (4), that is relevant to isopenicillin N synthase (IPNS) biomimicry. Cyclic voltammetry studies demonstrate the ligand's redox non‐innocence, where phenolate oxidation is the first electrochemical response observed in K‐L, 2 and 4. However, the first electrochemical oxidation in 1 is iron‐centred, the assignment of which is supported by DFT calculations. Overall, ImPh2NNOtBu provides access to well‐defined mononuclear, monoligated, N,N,O‐bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved.

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Language(s): eng - English
 Dates: 2020-12-162021-03-17
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.202004633
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 27 (16) Sequence Number: - Start / End Page: 5191 - 5204 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058