N,N,O Ligands Based on Triazoles and Transition Metal Complexes Thereof

Hübner, Eike G.; Fischer, Nina V.; Heinemann, Frank W.; Mitra, Utpal; Dremov, Viacheslav; Müller, Paul; Burzlaff, Nicolai

doi:10.1002/ejic.201000391

Cited by 17 publications

(4 citation statements)

References 32 publications

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“…We report the first series of ruthenium scorpionate complexes based upon 1,2,4-triazole ligands of varied steric bulk. Scorpionate , complexes of ruthenium have most commonly been based upon pyrazole (in Tp − and related complexes and N,N,O complexes − ) but have also been reported with 1,2,3-triazole derivatives, other N donor heterocycles, and S donors. − Many of these complexes are promising catalysts or form interesting structures. Specifically, C–H bond activation is catalyzed by various (Tp)Ru(arene) complexes, and complexes with agostic B–H to metal interactions have been reported. ,, Our work herein shows that 1,2,4-triazole-based scorpionate complexes are useful as base-free transfer hydrogenation catalysts, and they show new structural variations.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

et al. 2013

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The first ruthenium complexes of bulky tris(triazolyl)borate (Ttz) ligands were synthesized, fully characterized, and studied as transfer hydrogenation catalysts. The structures of the complexes were (η6-arene)RuCl(N,N), where in each case N,N is a κ2-Ttz or bis(triazolyl)borate (Btz) ligand (arene = p-cymene (1, 3, 5, 6), benzene (2), C6Me6 (4); N,N = TtzPh,Me* (1, 2), TtzMe,Me (3, 4), Ttz (5), Btz (6)). All but 5 were crystallographically characterized, and notably for 1 and 2 a rearranged ligand structure is observed (as indicated by an asterisk). These complexes were all effective catalysts for transfer hydrogenation of aryl ketones in isopropyl alcohol with base co-catalyst, with rates that were accelerated by moisture-free conditions. Complexes 1 and 2 are also effective catalysts for base-free transfer hydrogenation, and with 1 hydrogenation of several base-sensitive substrates was demonstrated. The ability of 1 to serve as a hydrogenation catalyst without base is attributed primarily to steric bulk, and a preliminary mechanism for formation of that active catalyst is proposed.

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Section: Introductionmentioning

confidence: 99%

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

et al. 2013

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“…As previously mentioned, this can be regarded as the most electronically and structurally faithful group with which to model the Numerous examples of N,N,O ligands can be found in the literature, where the nature of constituent donor groups has been systematically varied. [34][35][36][37] By modifying the two N-donors and any of their tethered organic substituents, the steric or electronic properties of the ligands can easily be tuned. In some cases, two different N-donors have been installed, thereby imparting chirality to the ligand scaffold.…”

Section: Carboxylate Ligandsmentioning

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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“…The use of ligands based on bis(triazol‐1‐yl)methane moieties in coordination chemistry has been scarcely reported. Bis(1H‐1,2,4‐triazol‐1yl)acetic acid and bis(2H‐benzotriazol‐2‐yl)acetic acid were the first ligands of this class reported, and their Ru, Mn, Cu and Ni complexes have found use in the synthesis of metal‐organic frameworks (MOF), in medicinal chemistry as mimics of the active site of metalloenzymes, as radiopharmaceuticals and anticancer agents [25‐30] . More recently, acetamidate and thioacetamidate heteroscorpionate ligands based on the bis(triazol‐1‐yl)methane moiety have been used for the synthesis of organometallic zinc compounds (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Design of New Bis(1,2,3‐triazol‐1‐yl)methane‐Based Nitrogen Ligands: Synthesis and Coordination Chemistry

Martínez de Sarasa Buchaca,

de la Cruz‐Martínez,

Naranjo

et al. 2024

Chemistry A European J

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The reaction between bis(1,2,3‐triazol‐1‐yl)methane derivatives and nBuLi and various aldehydes, yielded novel neutral ligand precursors incorporating alcohol functional groups. The resulting compounds exhibited distinct characteristics depending on the steric hindrance of the aldehyde employed. In instances where aromatic aldehydes were utilized, functionalization occurred at the methine group bridging both triazole rings. Conversely, the use of pivalic aldehyde prompted functionalization at the C5 position of the triazole ring. These compounds were subsequently employed as ligand precursors in the synthesis of organometallic aluminum and zinc complexes, yielding dinuclear complexes with high efficiency. The structural elucidation of all compounds was accomplished through spectroscopic methods and validated by X‐ray crystallography. Preliminary catalytic investigations into the coupling reaction of cyclohexene oxide and CO2 revealed that aluminum and zinc complexes catalyzed the selective formation of polyether and polycarbonate materials, respectively.

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N,N,O Ligands Based on Triazoles and Transition Metal Complexes Thereof

Cited by 17 publications

References 32 publications

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

Ruthenium Complexes of Triazole-Based Scorpionate Ligands Transfer Hydrogen to Substrates under Base-Free Conditions

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

Design of New Bis(1,2,3‐triazol‐1‐yl)methane‐Based Nitrogen Ligands: Synthesis and Coordination Chemistry

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