Synthesis and characterization of a gold(<scp>i</scp>) bis(triazolylidene) complex featuring a large [(Tp<sup>Me2</sup>)<sub>2</sub>K] anion

Priante-Flores, Armando; Salazar‐Pereda, Verónica; Rheingold, Arnold L.; Mendoza‐Espinosa, Daniel

doi:10.1039/c8nj03318h

Cited by 7 publications

(2 citation statements)

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“…Due to their Lewis acidic nature, gold(I) complexes are prone to activate alkynes, alkenes, and allenes , and have proven to be active in hydroamination reactions. ,,,− Herein we focus on the intermolecular hydroamination of alkynes through primary amines. Various gold complexes with phosphine − ,, and NHC − ligands have been studied in this regard.…”

Section: Introductionsupporting

confidence: 61%

“…The reaction of phenylacetylene with aniline was chosen as the model reaction (Table ). It has been shown that phenoxy- and benzoxy-linked 1,2,3-triazolylidene and ring-fused benzoxazine-derived 1,2,3-triazolylidene gold(I) chloride complexes are potent precatalysts in this reaction. ,, In those studies a silver salt was applied as a halide scavenger. We investigated the applicability of the MIC gold complexes in a silver-free catalytic system to avoid the potential catalytic activity of the silver species or the possible interaction of the gold species with the silver salts …”

Section: Resultsmentioning

confidence: 99%

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Spotlight on Ligand Effects in 1,2,3-Triazolylidene Gold Complexes for Hydroamination Catalysis: Synthesis and Catalytic Application of an Activated MIC Gold Triflimide Complex and Various MIC Gold Chloride Complexes

et al. 2021

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The control of catalytic properties through ligand design is at the heart of homogeneous catalysis. Herein we report on ligand effects in six 1,3,4-substituted 1,2,3-triazolylidene gold complexes as precatalysts for the intermolecular hydroamination catalysis of alkynes with amines. Mainly silver-free protocols have been followed for the synthesis of the complexes and for the catalytic reactions. All of the novel gold complexes have been fully characterized, one of them being, to the best of our knowledge, the first 1,2,3-triazolylidene-based mesoionic carbene (MIC) gold complex with a weakly coordinating second ligand. In contrast to expectations, the gold complexes bearing the most strongly electron donating MICs did not display the best conversion in catalysis. According to our investigations the stability of the complex is a determining factor in the present case. The MIC gold bistriflimide complex shows activity in hydroamination catalysis without the need for an activating additive.

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Section: Introductionsupporting

confidence: 61%

Section: Resultsmentioning

confidence: 99%

Spotlight on Ligand Effects in 1,2,3-Triazolylidene Gold Complexes for Hydroamination Catalysis: Synthesis and Catalytic Application of an Activated MIC Gold Triflimide Complex and Various MIC Gold Chloride Complexes

et al. 2021

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Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Beerhues

Neubrand

Sobottka

et al. 2021

Chemistry A European J

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Carbene‐based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3‐triazolylidene selenium adducts are reported. It is found that the half‐wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene‐based mesoionic carbenes (MICs). Furthermore, unexpected quasi‐reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene‐type MIC‐gold phenyl complex resulting in a MIC‐radical coordinated AuI species. Apart from UV‐Vis‐NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold‐coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene‐based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.

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Synthesis and Catalytic Applications of Multinuclear Gold(I)‐1,2,3‐Triazolylidene Complexes

2021

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A series of mono‐ to trinuclear gold(I) complexes (1–3) supported by oxo‐functionalized 1,2,3‐triazolylidenes have been prepared. All new compounds were fully characterized by means of 1H and 13C NMR spectroscopy, elemental analyses, and in the case of complexes 1 and 2 by x‐ray diffraction. The catalytic performance of the new triazolylidene gold complexes was tested in several hydroelementation and cyclization processes employing a variety of alkynes as starting materials. According to the overall results, the trinuclear complex 3 displayed the highest catalytic activity in all processes, providing good to excellent yields under mild reaction conditions.

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Synthesis and characterization of a gold(i) bis(triazolylidene) complex featuring a large [(Tp^Me2)₂K] anion

Abstract: We report the synthesis, charaterization and catalytic performance of a unique bis(triazolylidene) gold(i) complex featuring a large [(TpMe2)2K] anion.

Cited by 7 publications

References 60 publications

Spotlight on Ligand Effects in 1,2,3-Triazolylidene Gold Complexes for Hydroamination Catalysis: Synthesis and Catalytic Application of an Activated MIC Gold Triflimide Complex and Various MIC Gold Chloride Complexes

Spotlight on Ligand Effects in 1,2,3-Triazolylidene Gold Complexes for Hydroamination Catalysis: Synthesis and Catalytic Application of an Activated MIC Gold Triflimide Complex and Various MIC Gold Chloride Complexes

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Synthesis and Catalytic Applications of Multinuclear Gold(I)‐1,2,3‐Triazolylidene Complexes

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Synthesis and characterization of a gold(i) bis(triazolylidene) complex featuring a large [(TpMe2)2K] anion

Abstract: We report the synthesis, charaterization and catalytic performance of a unique bis(triazolylidene) gold(i) complex featuring a large [(TpMe2)2K] anion.

Cited by 7 publications

References 60 publications

Spotlight on Ligand Effects in 1,2,3-Triazolylidene Gold Complexes for Hydroamination Catalysis: Synthesis and Catalytic Application of an Activated MIC Gold Triflimide Complex and Various MIC Gold Chloride Complexes

Spotlight on Ligand Effects in 1,2,3-Triazolylidene Gold Complexes for Hydroamination Catalysis: Synthesis and Catalytic Application of an Activated MIC Gold Triflimide Complex and Various MIC Gold Chloride Complexes

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Synthesis and Catalytic Applications of Multinuclear Gold(I)‐1,2,3‐Triazolylidene Complexes

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Synthesis and characterization of a gold(i) bis(triazolylidene) complex featuring a large [(Tp^Me2)₂K] anion

Directed Design of a Au^I Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations