Gold(I) and gold(III) complexes of 1,2,4-triazole-derived N-heterocyclic carbenes: Synthesis, characterization, in-vitro anticancer and anti-inflammatory studies

Phung, Hai; Vu, Heather; Ly, Mary; Nguyen, Hung Huy; Nguyen, Thu Hang; Luong, Huyen T.T.; Nguyễn, Vân Hà

doi:10.1016/j.inoche.2023.110898

Cited by 7 publications

(1 citation statement)

References 65 publications

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“…, 1,2,4-triazol-5-ylidenes), which can be regarded as imidazol-2-ylidene analogues with an additional nitrogen atom inserted in the ring, are less explored 8,9 even though they are equally structurally versatile and widely applicable. Thus far, 1,2,4-triazolylidenes have been used as auxiliary ligands in the design of transition metal catalysts, 10 new luminescent materials 11 and biologically active compounds, 12 and further utilised as organocatalysts. 13…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis and bonding of 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes

Franc,

Schulz,

Štěpnička

2024

Dalton Trans.

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Section: Introductionmentioning

confidence: 99%

Facile synthesis and bonding of 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes

Franc,

Schulz,

Štěpnička

2024

Dalton Trans.

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Oxidation State and Halogen Influence on the NHC‐Gold‐Halide‐Catalyzed Cyclization of Propargylic Amides

Sargentoni,

Galassi,

Luciani

et al. 2024

Adv Synth Catal

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The homogeneously catalyzed cycloisomerization reaction of propargylic amides was tested as benchmark reaction for two homologous series of Au(I) and Au(III) complexes with NHC ligands. This reaction is known to afford either aromatic oxazoles or dihydrooxazoles, depending on the oxidation state of the applied gold catalysts. For this purpose, symmetric and unsymmetric NHC ligands with mixed alkyl or benzyl substituents (1,3‐dimethyl‐imidazolyl‐2yl or 1‐benzyl‐3‐methyl‐imidazolyl‐2‐yl) and the corresponding Au(I) and Au(III) derivatives were prepared and characterized by analytical methods, IR and 1H and 13C NMR spectroscopies, and by X‐ray diffraction methods. Ten NHC‐gold(I) and NHC‐gold(III) complexes were tested on the cyclization reactions by adding gold catalysts in the presence and absence of AgPF6. Noteworthy, only the 1‐benzyl‐3‐methyl‐gold(III) trichloride was able to give selectively the aromatic oxazole without the addition of the silver salt. Interestingly, on contrary to what is reported in the literature, the use of gold(I) or gold(III) complexes does not influence the chemoselectivity of the cyclization reaction, while the halide bound to the metal does. In this regard, a mechanism purposing the dihydrooxazole as an intermediate for the formation of aromatic oxazole is proposed.

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Advancing Gold Redox Catalysis: Mechanistic Insights, Nucleophilicity‐Guided Transmetalation, and Predictive Frameworks for the Oxidation of Aryl Gold(I) Complexes

Shiri,

Ho,

Bissember

et al. 2023

Chemistry A European J

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Gold redox catalysis, often facilitated by hypervalent iodine(III) reagents, offers unique reactivity but its progress is mainly hindered by an incomplete mechanistic understanding. In this study, we investigated the reaction between the gold(I) complexes [(aryl)Au(PR3)] and the hypervalent iodine(III) reagent PhICl2, both experimentally and computationally and provided an explanation for the formation of divergent products as the ligands bonded to the gold(I) center change. We tackled this essential question by uncovering an intriguing transmetalation mechanism that takes place between gold(I) and gold(III) complexes. We found that the ease of transmetalation is governed by the nucleophilicity of the gold(I) complex, [(aryl)Au(PR3)], with greater nucleophilicity leading to a lower activation energy barrier. Remarkably, transmetalation is mainly controlled by a single orbital – the gold dx2−y2 orbital. This orbital also has a profound influence on the reactivity of the oxidative addition step. In this way, the fundamental mechanistic basis of divergent outcomes in reactions of aryl gold(I) complexes with PhICl2 was established and these observations are reconciled from first principles. The theoretical model developed in this study provides a conceptual framework for anticipating the outcomes of reactions involving [(aryl)Au(PR3)] with PhICl2, thereby establishing a solid foundation for further advancements in this field.

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Gold(I) and gold(III) complexes of 1,2,4-triazole-derived N-heterocyclic carbenes: Synthesis, characterization, in-vitro anticancer and anti-inflammatory studies

Cited by 7 publications

References 65 publications

Facile synthesis and bonding of 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes

Facile synthesis and bonding of 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes

Oxidation State and Halogen Influence on the NHC‐Gold‐Halide‐Catalyzed Cyclization of Propargylic Amides

Advancing Gold Redox Catalysis: Mechanistic Insights, Nucleophilicity‐Guided Transmetalation, and Predictive Frameworks for the Oxidation of Aryl Gold(I) Complexes

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