Mechanochemical synthesis of Cu(<scp>i</scp>)-N-heterocyclic carbene complexes

Pisanò, Gianmarco; Cazin, Catherine S. J.

doi:10.1039/d0gc01923b

Cited by 36 publications

(33 citation statements)

References 51 publications

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“…Furthermore, in the case of gold and copper, one‐pot syntheses of the desired CMA compounds were successfully carried out directly from the imidazolium salt and metal sources. In order to showcase potential further improvements and inspired by previous advances in mechanochemical synthesis of Cu−NHC complexes, [29] we also performed a mechanochemical, solvent‐free, high‐yielding synthesis of 6 a in a planetary ball‐mill, with a reaction time of 30 minutes (Scheme 3 ) to demonstrate an initial proof‐of‐concept using solvent‐free methods. This is currently being further investigated in our laboratories.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, we were intrigued by the possibility of providing a simplified and general synthetic protocol to access photoactive CMAs of Cu, Ag and Au bearing various carbene‐type ligands, studying the excited state properties of new complexes and showcasing their application in photocatalysis. As a starting point, the use of a mild, cost‐efficient and robust base should be sought to render the synthesis amenable to operationally simpler and milder conditions, as we have demonstrated in a number of recent reports [24b,28,29] …”

Section: Introductionmentioning

confidence: 99%

“…As a starting point, the use of a mild, cost‐efficient and robust base should be sought to render the synthesis amenable to operationally simpler and milder conditions, as we have demonstrated in a number of recent reports. [ 24b , 28 , 29 ]…”

Section: Introductionmentioning

confidence: 99%

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Simple Synthetic Routes to Carbene‐M‐Amido (M=Cu, Ag, Au) Complexes for Luminescence and Photocatalysis Applications

Tzouras

Martynova

et al. 2021

Chemistry A European J

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The development of novel and operationally simple synthetic routes to carbene‐metal‐amido (CMA) complexes of copper, silver and gold relevant for photonic applications are reported. A mild base and sustainable solvents allow all reactions to be conducted in air and at room temperature, leading to high yields of the targeted compounds even on multigram scales. The effect of various mild bases on the N−H metallation was studied in silico and experimentally, while a mechanochemical, solvent‐free synthetic approach was also developed. Our photophysical studies on [M(NHC)(Cbz)] (Cbz=carbazolyl) indicate that the occurrence of fluorescent or phosphorescent states is determined primarily by the metal, providing control over the excited state properties. Consequently, we demonstrate the potential of the new CMAs beyond luminescence applications by employing a selected CMA as a photocatalyst. The exemplified synthetic ease is expected to accelerate the applications of CMAs in photocatalysis and materials chemistry.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Simple Synthetic Routes to Carbene‐M‐Amido (M=Cu, Ag, Au) Complexes for Luminescence and Photocatalysis Applications

Tzouras

Martynova

et al. 2021

Chemistry A European J

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“…Therefore, a microreactor charged only with potassium carbonate was injected with a 0.03 m solution of the cuprate species [IPrH][CuCl 2 ]. Note here that the cuprate obtained by mechanochemistry [14] or by simply pre‐mixing the imidazolium salt (IPr⋅HCl) and CuCl (5 min at RT in green acetone) [7d] are both fit for purpose. Gratifyingly, in both scenarios, the cuprate species was completely converted into the final complex by reaction with potassium carbonate, using the same operating conditions as before (5 min at 50 °C).…”

Section: Figurementioning

confidence: 99%

“…To this end, we took inspirationf rom mechanistic insights afforded by someo fo ur recent studies [7] focusingo nt he weak base route. The identification of av ery simply formed ate complex (when the metal source is placed into contact with the imidazolium salt) raised the possibilityo f using this cuprate, which can be made by grinding or milling, [14] as ar eagent already containing the metal and the imidazolium components in the correct ratio and deploying it in the flow reaction.…”

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confidence: 99%

Continuous Flow Synthesis of Metal–NHC Complexes**

Simoens

Scattolin

Cauwenbergh

et al. 2021

Chemistry A European J

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The use of weakb ases and mild conditions is currently the most sustainable and attractive synthetica pproach for the preparation of late-transition metal complexes, some of which are widely used in catalysis, medicinal chemistry and materials science.H erein, the use of cuprate, aurate or palladate speciesf or ac ontinuous flow preparation of Cu I ,A u I and Pd II-NHC complexes is reported. All reactions examined proceed under extremely mild conditions and make use of technicalg rade acetonea s solvent. The scalability of the process was exemplified in a multigram-scale synthesis of [Cu(IPr)Cl]. N-Heterocyclic carbenes (NHCs) have become am ost popular ligand family for the synthesis of organometallic compounds with uses in catalysis. [1] The surprising stabilityo ft he metal-NHC bond has also permitted the study and use of transition metal-NHC complexes in medicinal chemistry [2] and mostr ecently in materials science. [3] The nowadays ubiquitousu se of this fascinating class of ligandsh as been ad riving force encouraging the development of sustainable, efficient and userfriendly routes leadingt otheir syntheses. [4] Although not quite sustainable, the most commonly used synthetic strategy,b ased on the seminal work of Arduengo, [5] involves the generation of free NHC by deprotonation of the corresponding azolium salt with as trong base (e.g. NaH, KOtBu)a nd subsequent coordination to am etal. The most significant drawbacks of the free carbene route lies in the need for strictly anhydrous conditions. Additionally,t his route is not suitable for complexes requiring the use of metal precursors sensitivet ostrong bases.

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Mechanochemical synthesis of half‐sandwich iridium/rhodium complexes with 8‐hydroxyquinoline derivatives ligands

Jia

Zhi

et al. 2022

Applied Organom Chemis

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Mechanochemistry provides a rapid, efficient route to half‐sandwich iridium and rhodium complexes from [MCp*(μ‐Cl)Cl]2 (M = Ir, Rh) and 8‐hydroxyquinoline‐2‐carbaldehyde without the need for Schlenk manipulation, inert gas protection, or dry solvents. Furthermore, post‐synthetic modification of the half‐sandwich metal complexes has been carried out via a mechanochemical Wittig reaction between half‐sandwich metal complex and phosphorus ylide. All complexes were fully characterized by 1H and 13C NMR spectra, infrared spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction method. The half‐sandwich rhodium complexes exhibited high catalytic activity towards the amide synthesis between aldehyde and hydroxylamine hydrochloride (NH2OH·HCl) with a broad functional group tolerance.

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Mechanochemical synthesis of Cu(i)-N-heterocyclic carbene complexes

Abstract: A versatile mechanosynthetic approach to NHC-Cu complexes is reported.

Cited by 36 publications

References 51 publications

Simple Synthetic Routes to Carbene‐M‐Amido (M=Cu, Ag, Au) Complexes for Luminescence and Photocatalysis Applications

Simple Synthetic Routes to Carbene‐M‐Amido (M=Cu, Ag, Au) Complexes for Luminescence and Photocatalysis Applications

Continuous Flow Synthesis of Metal–NHC Complexes**

Mechanochemical synthesis of half‐sandwich iridium/rhodium complexes with 8‐hydroxyquinoline derivatives ligands

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