Design and synthesis of a series of facially coordinating tridentate ligands containing an N2O donor atom set

Jameson, Donald L.; Hilgen, S. E.; Hummel, Conrad E.; Pichla, Susan L.

doi:10.1016/s0040-4039(00)99533-9

Cited by 19 publications

(20 citation statements)

References 5 publications

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“…Ligand H-Im Ph2 NNO tBu can be readily synthesised in five steps using ap rocedure adapted from Jameson et al (Scheme 1). [25,37] An additional alkylation steph as been incorporated to install tert-butyl substituents on the phenolate ring. [38] The synthesis also involves the use of 1-methyl-4,5-diphenylimidazole instead of the sterically less encumbered 1methylimidazole, as our group has previously demonstrated that ah igherd egree of substitutiono nt he imidazole favours the formation of monoligated complexes.…”

Section: Ligand Synthesis and Characterisationmentioning

confidence: 99%

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

Monkcom

Bruin

Vries

et al. 2021

Chemistry A European J

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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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Section: Ligand Synthesis and Characterisationmentioning

confidence: 99%

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

Monkcom

Bruin

Vries

et al. 2021

Chemistry A European J

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“…Tripodal bis(pyrazolyl)methanes, as members of the greater family of poly(pyrazolyl)methanes, have served as excellent ligands in coordination chemistry since they were established in 1987 by Byers et al The first compounds were the N , N,N ‐ligands HC(Pz) 2 (Py) and HC(Pz) 2 (Mim), containing one pyridinyl or one methylimidazolyl unit besides the two pyrazolyls. Jameson et al synthesized the ligand (2‐hydroxyphenyl)bis(pyrazolyl)methane as the first N , N , O ‐ligand . In 1990 thienyl was the first S‐donor function added to the ligand system, leading to the N , N , S ‐ligand HC(Pz) 2 (Thi) .…”

Section: Introductionmentioning

confidence: 99%

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

Herber

Moegling

Siris

et al. 2018

Zeitschrift anorg allge chemie

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The ligand class of tridentate bis(pyrazolyl)methanes was extended via the syntheses of HC(3,5‐EtPz)2Py. This ligand is the first of its kind with a homogeneous 3,5‐functionalization with large substituents. On the basis of 3,5‐functionalized ligands we were able to synthesize 15 novel complexes with FeII, ZnII, and CuII salts. Herein we present an extensive coordination chemistry study, that focuses on the influences of different metals, ligands, and counterions on the coordination mode and on the spin state in case of FeII complexes.

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“…In another study, [48] similar zinc complexes of the type [Zn II (L) 2 ] (4 and 5) were obtained by reacting L1 or L3 in a 2:1 stoichiometry with ZnCl 2 in methanol (Fig. 7, top).…”

Section: The Evolution Of Baip Facial Nno Ligandsmentioning

confidence: 90%

“…The carboxylic acid ligands can conveniently be synthesised from the hydrolysis of the ester ligands. Phenol ligands are also conveniently synthesised from different 1-alkyl(benz)imidazole precursors, using a synthetic route previously described by Jameson et al [48] The synthesis starts with the deprotonation of imidazole using n-BuLi, after which the lithium imidazolium salt is reacted with a hydroxy-protected methyl salicylate in a 2:1 stoichiometry. The resulting tertiary alcohol (D) is subsequently methylated (E), before deprotection of the phenol, thereby ensuring that the phenol is the only site that can be deprotonated for subsequent coordination chemistry.…”

Section: Synthesismentioning

confidence: 99%

Bioinspired Non-Heme Iron Complexes: The Evolution of Facial N, N, O Ligand Design

Monkcom¹,

Ghosh²,

Folkertsma³

et al. 2020

Chimia

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Iron-containing metalloenzymes that contain the 2-His-1-Carboxylate facial triad at their active site are well known for their ability to activate molecular oxygen and catalyse a broad range of oxidative transformations. Many of these reactions are synthetically challenging, and developing small molecular iron-based catalysts that can achieve similar reactivity and selectivity remains a long-standing goal in homogeneous catalysis. This review focuses on the development of bioinspired facial N,N,O ligands that model the 2-His-1-Carboxylate facial triad to a greater degree of structural accuracy than many of the polydentate N-donor ligands commonly used in this field. By developing robust, well-defined N,N,O facial ligands, an increased understanding could be gained of the factors governing enzymatic reactivity and selectivity.

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Design and synthesis of a series of facially coordinating tridentate ligands containing an N2O donor atom set

Cited by 19 publications

References 5 publications

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

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

A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

Bioinspired Non-Heme Iron Complexes: The Evolution of Facial N, N, O Ligand Design

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Design and synthesis of a series of facially coordinating tridentate ligands containing an N2O donor atom set

Cited by 19 publications

References 5 publications

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

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

A Study on FeII, ZnII and CuII Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands

Bioinspired Non-Heme Iron Complexes: The Evolution of Facial N, N, O Ligand Design

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A Study on Fe^II, Zn^II and Cu^II Complexes with Novel Tridentate Bis(pyrazolyl)methane Ligands