Transition metal complexes of click-derived 1,2,3-triazoles as catalysts in various transformations: An overview and recent developments

Joseph, Moegamat Cassiem; Swarts, Avril; Mapolie, Selwyn F.

doi:10.1016/j.ccr.2023.215317

Cited by 17 publications

(4 citation statements)

References 140 publications

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“…The reaction mechanism of copper‐catalyzed triazole ring formation involving one copper atom is shown in Figure 3 60–63 . Copper acetylide is formed at the outset, and this is followed by coordination of the copper ion with the organic azide.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, DFT calculations, and investigation of catalytic and biological activities of back‐bond functionalized re‐NHC‐Cu complexes

Yagmurlu,

Buğday,

Yaşar

et al. 2024

Applied Organom Chemis

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Five copper complexes (3a–e) stabilized by ring‐expanded back‐bond functionalized N‐heterocyclic carbene ligands (re‐NHCs) were produced in the glovebox by reacting free re‐NHC with CuI precursor. The potential of these re‐NHC‐Cu complexes as catalysts on the synthesis of mono‐ and di‐(1,4‐disubstituted‐1,2,3‐triazoles) by Cu‐catalyzed azide–alkyne cycloaddition (CuAAC) reactions was investigated. Various spectroscopic approaches were utilized to completely characterize the structures of the re‐Cu‐NHC complexes. Furthermore, density functional theory (DFT) calculations were carried out to get further insights into their molecular geometry and CuAAC reaction mechanism. The re‐NHC‐Cu complexes showed high activity on the CuAAC reaction in an open‐air atmosphere at rt. The Gibbs free energies as well as the optimized geometries of the intermediates and the transition states of the determining step of the reactions catalyzed by 3a, 3e, and 3b complexes were computed. Complex 3e was found to be the most efficient catalyst among these re‐NHC‐Cu complexes. Additionally, re‐Cu‐NHC complexes were investigated for their biological activities, including antiproliferative, antioxidant, AChE and TyrE inhibition, and antiparasitic activity. The results showed that the 3b, 3d, and 3e complexes possessed strong antiproliferative activity against human colon carcinoma (HCT‐116) and moderate cytotoxic activity against hepatocellular carcinoma (HepG‐2) cell lines. In addition, effective selective antileishmanial effects were observed for the 3e compound against both promastigotes and amastigotes stages of L. major with an IC50 value of 0.027 and 0.39 μM mL−1, respectively. These results demonstrate that these compounds are promising candidates for the treatment of colorectal cancer and leishmaniasis.

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Section: Resultsmentioning

confidence: 99%

Synthesis, DFT calculations, and investigation of catalytic and biological activities of back‐bond functionalized re‐NHC‐Cu complexes

Yagmurlu,

Buğday,

Yaşar

et al. 2024

Applied Organom Chemis

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“…Following the relative basicity order, N-3 of the 1,2,3-triazole ring coordinates preferentially to the metal center. [39][40] The two alternative pre-reactive complexes are show in Figure 1, together with their relative energies.…”

Section: General Aspectsmentioning

confidence: 99%

Mechanistic insights into C(sp2)-H activation in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives: a theoretical study with palladium acetate catalyst

Fogos,

Lessa,

de Carvalho da Silva

et al. 2024

J Mol Model

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ContextThe activation of C-H bonds is a fundamental process in synthetic organic chemistry, which enables their replacement by highly reactive functional groups. Coordination compounds serve as effective catalysts for this purpose, as they facilitate chemical transformations by interacting with C-H bonds. A comprehensive understanding of the mechanism of activation of this type of bond lays the foundation for the development of e cient protocols for cross-coupling reactions. We explored the activation of C(sp 2 )-H bonds in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives with CH 3 , OCH 3 and NO 2 substituents in the para position of the phenyl ring, using palladium acetate as catalyst. The studied reaction is the rst step for subsequent conjugation of the triazoles with naphthoquinones in a Heck-type reaction to create a C-C bond. The basic nitrogen atoms of the 1,2,3-triazole coordinate preferentially with the cationic palladium center to form an activated species. A concerted proton transfer from the terminal vinyl carbon to one of the acetate ligands with low activation energy is the main step for the C(sp 2 )-H activation. This study offers signi cant mechanistic insights for enhancing the effectiveness of C(sp 2 )-H activation protocols in organic synthesis. MethodsAll calculations were performed using the Gaussian 09 software package and density functional theory (DFT). The structures of all reaction path components were fully optimized using the CAM-B3LYP functional with the Def2-SVP basis set. The optimized geometries were analyzed by computing the second-order Hessian matrix to con rm whether the corresponding structure is a minimum or a true transition state. To account for solvent effects, the Polarizable Continuum Model of the Integral Equation Formalism (IEFPCM) with water as the solvent was used.

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“…16 The electronic effects imparted by these ligands also led to the unprecedented observation of photochemical ligand ejection from an osmium(II) complex, [Os(btz) 3 ] 2+ . 37 In the vast majority of 1,2,3-triazole-based complexes coordination to the metal occurs through the more basic N3-position 38,39 but can be induced to coordinate through the N2 atom through chelation. 40−42 We have shown that while the 4-(pyrid-2-yl)-1,2,3-triazole (pytz) complex [Ru-(bpy) 2 (pytz)] 2+ (Figure 1) is only moderately photochemically reactive, the corresponding complex of the inverted pytz ligand 1-(pyrid-2-yl)-1,2,3-triazole (pytz inv ) is far more photochemically reactive.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In the vast majority of 1,2,3-triazole-based complexes coordination to the metal occurs through the more basic N3-position , but can be induced to coordinate through the N2 atom through chelation. − We have shown that while the 4-(pyrid-2-yl)-1,2,3-triazole (pytz) complex [Ru(bpy) 2 (pytz)] 2+ (Figure ) is only moderately photochemically reactive, the corresponding complex of the inverted pytz ligand 1-(pyrid-2-yl)-1,2,3-triazole (pytz inv ) is far more photochemically reactive . This prompted us to further investigate the photochemistry of complexes in which triazole donors are constrained to coordinate through the N2 atom of the triazole ring.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates

Eastham,

Kennedy,

Scottwell

et al. 2024

Inorg. Chem.

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Photochemical ligand release from metal complexes may be exploited in the development of novel photoactivated chemotherapy agents for the treatment of cancer and other diseases. Highly intriguing photochemical behavior is reported for two ruthenium(II) complexes bearing conformationally flexible 1,2,3triazole-based ligands incorporating a methylene spacer to form 6membered chelate rings. [Ru(bpy) 2 (pictz)] 2+ (1) and [Ru-(bpy) 2 (btzm)] 2+ (2) (bpy = 2,2′-bipyridyl; pictz = 1-(picolyl)-4phenyl-1,2,3-triazole; btzm = bis(4-phenyl-1,2,3-triazol-4-yl)methane) exhibit coordination by the triazole ring through the less basic N2 atom as a consequence of chelation and readily undergo photochemical release of the pictz and btzm ligands (ϕ = 0.079 and 0.091, respectively) in acetonitrile solution to form cis-[Ru-(bpy) 2 (NCMe) 2 ] 2+ (3) in both cases. Ligand-loss intermediates of the form [Ru(bpy) 2 (κ 1 -pictz or κ 1 -btzm)(NCCD 3 )] 2+ are detected by 1 H NMR spectroscopy and mass spectrometry. Photolysis of 1 yields three ligand-loss intermediates with monodentate pictz ligands, two of which form through simple decoordination of either the pyridine or triazole donor with subsequent solvent coordination (4-tz (N2) and 4-py, respectively). The third intermediate, shown to be able to form photochemically directly from 1, arises through linkage isomerism in which the monodentate pictz ligand is coordinated by the triazole N3 atom (4-tz (N3) ) with a comparable ligand-loss intermediate with an N3-bound κ 1 -btzm ligand also observed for 2.

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Transition metal complexes of click-derived 1,2,3-triazoles as catalysts in various transformations: An overview and recent developments

Cited by 17 publications

References 140 publications

Synthesis, DFT calculations, and investigation of catalytic and biological activities of back‐bond functionalized re‐NHC‐Cu complexes

Synthesis, DFT calculations, and investigation of catalytic and biological activities of back‐bond functionalized re‐NHC‐Cu complexes

Mechanistic insights into C(sp2)-H activation in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives: a theoretical study with palladium acetate catalyst

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates

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