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

Monkcom, Emily C.; de Bruin, Daniël; de Vries, Annemiek J.; Lutz, Martin; Ye, Shengfa; Klein Gebbink, Robertus J. M.

doi:10.1002/chem.202004633

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

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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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Citation

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

Abstract

We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, Im^Ph2NNO^tBu (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, Im^Ph2NNO^tBu provides access to well‐defined mononuclear, monoligated, N,N,O‐bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved.