Reversible Oxidation of Copper(I) Iodide in the Presence of Imidazole

Goodgame, D. M. L.; Goodgame, M.; Canham, G. W. Rayner

doi:10.1038/222866a0

Cited by 13 publications

(8 citation statements)

References 3 publications

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“…With both Cu II and Cu I precatalysts, the reaction is highly solvent dependent, with the best yields and selectivities obtained in DMF. 9 As shown in Figure 1 , the initial rate of product formation in DMF at 60 °C is slightly faster with Cu(OTf)(CH 3 CN) 4 than with Cu(OTf) 2 .…”

Section: Resultsmentioning

confidence: 84%

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the Cu^I/Cu^III Manifold in Copper Catalysis

et al. 2014

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A combination of experimental and density functional theory (DFT) investigations suggests that the Cu-catalyzed fluorination of unsymmetrical diaryliodonium salts with general structure [Mes(Ar)I]+ in N,N′-dimethylformamide proceeds through a CuI/CuIII catalytic cycle. A low concentration of fluoride relative to combined iodonium reagent plus copper ensures that [Mes(Ar)I]+ is available as the reactive species for oxidative “Ar+” transfer to a CuI center containing one or two fluoride ligands. A series of different possible CuI active catalysts (containing fluoride, triflate, and DMF ligands) have been evaluated computationally, and all show low-energy pathways to fluorinated products. The oxidation of these CuI species by [Mes(Ar)I]+ to form cis-Ar(F)CuIII intermediates is proposed to be rate-limiting in all cases. Ar–F bond-forming reductive elimination from CuIII is computed to be very facile in all of the systems examined. The conclusions of the DFT experiments are supported by several experimental studies, including tests showing that CuI is formed rapidly under the reaction conditions and that the fluoride concentration strongly impacts the reaction yields/selectivities.

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Section: Resultsmentioning

confidence: 84%

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the Cu^I/Cu^III Manifold in Copper Catalysis

et al. 2014

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“…) 14 (2) Cl SB 4455 (3) 315 ( 4) 3442 (3) 36 (3) 86 ( 4) 70( 4) 4 (3) -1 (3) 19 (3) C19B 3156 (3) 168 (3) 2351 (2) 32 (3) 51 (3) 57 (3) 6 (2) 13 (2) 15 (3) C20B 2233 (3) 363 (3) 2025 (2) 37 (3) 56 (3) 38 (3) 1 (2) 9 (2) 6 (2…”

Section: C12bunclassified

“…-626 (2) 2747 (2) 33 (2) 51 (3) 37 (2) -1 (2) 6 (2) 11 (2) 04 C 421 (20) -1756 (19) 412 ( 14 62( 4) 50 (3) 8 ( 2) 15 (2) 16 (3)…”

Section: C12bunclassified

Reaction of molecular oxygen with copper(I). Structural characterization of dimeric .mu.-carbonato and tetrameric .mu.-hydroxo complexes resulting from the autoxidation of a copper(I) carbonyl complex

Gagné¹,

Gall²,

Lisensky³

et al. 1979

Inorg. Chem.

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“…In general, the presence of catalytically active copper (I) leads to an increase in instability of the chemical content on the catalyst surface due to interaction with molecular oxygen and copper oxide formation [30]. To protect the surface of catalytically active copper (I) compound CuI, the synthesis of composites where copper iodide is included into the porous polymeric framework could be a promising strategy.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Synthesis of Copper Iodide-Polypyrrole Nanocomposites

et al. 2021

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A novel one-pot chemical synthesis of functional copper iodide-polypyrrole composites, CuI-PPy, has been proposed. The fabrication process allows the formation of nanodimensional metal salt/polymer hybrid structures in a fully controlled time- and concentration-dependent manner. The impact of certain experimental conditions, viz., duration of synthesis, sequence of component addition and concentrations of the intact reagents on the structure, dimensionality and yield of the end-product was evaluated in detail. More specifically, the amount of marshite CuI within the hybrid composite can be ranged from 60 to 90 wt.%, depending on synthetic conditions (type and concentration of components, process duration). In addition, the conditions allowing the synthesis of nano-sized CuI distributed inside the polypyrrole matrix were found. A high morphological stability and reproducibility of the synthesized nanodimensional metal-polymer hybrid materials were approved. Finally, the electrochemical activity of the formed composites was verified by cyclic voltammetry studies. The stability of CuI-PPy composite deposited on the electrodes was strongly affected by the applied anodic limit. The proposed one-pot synthesis of the hybrid nanodimensional copper iodide-polypyrrole composites is highly innovative, meets the requirements of Green Chemistry and is potentially useful for future biosensor development. In addition, this study is expected to generally contribute to the knowledge on the hybrid nano-based composites with tailored properties.

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Reversible Oxidation of Copper(I) Iodide in the Presence of Imidazole

Cited by 13 publications

References 3 publications

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the Cu^I/Cu^III Manifold in Copper Catalysis

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the Cu^I/Cu^III Manifold in Copper Catalysis

Reaction of molecular oxygen with copper(I). Structural characterization of dimeric .mu.-carbonato and tetrameric .mu.-hydroxo complexes resulting from the autoxidation of a copper(I) carbonyl complex

One-Pot Synthesis of Copper Iodide-Polypyrrole Nanocomposites

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Reversible Oxidation of Copper(I) Iodide in the Presence of Imidazole

Cited by 13 publications

References 3 publications

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the CuI/CuIII Manifold in Copper Catalysis

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the CuI/CuIII Manifold in Copper Catalysis

Reaction of molecular oxygen with copper(I). Structural characterization of dimeric .mu.-carbonato and tetrameric .mu.-hydroxo complexes resulting from the autoxidation of a copper(I) carbonyl complex

One-Pot Synthesis of Copper Iodide-Polypyrrole Nanocomposites

Contact Info

Product

Resources

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Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the Cu^I/Cu^III Manifold in Copper Catalysis

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the Cu^I/Cu^III Manifold in Copper Catalysis