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Journal Article

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


Ye,  Shengfa
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences;
Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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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.

Cite as: https://hdl.handle.net/21.11116/0000-0008-3170-2
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.