Recent advances in the chemistry and applications of N-heterocyclic carbenes

Bellotti, Peter; Koy, Maximilian; Hopkinson, Matthew N.; Glorius, Frank

doi:10.1038/s41570-021-00321-1

Cited by 436 publications

(237 citation statements)

References 168 publications

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“…While for Cu (111), the regular bare areas on the 0.6 ML sample provide enough space for reactive adsorption. We are confident that such regular structures, especially the controllable ratio of surface to volume caused by conformational switching, will be of great importance in constructing patterned supramolecular assembly carbene structures [37, 47, 48] for future applications in catalysis and beyond [8, 23] …”

Section: Discussionmentioning

confidence: 99%

“…Since the seminal report by Arduengo et al., [1] N‐heterocyclic carbenes (NHCs) have fostered considerable interest in catalysis, [2–4] as ligands for p‐block elements [5] and transition metals, [6] thanks to their unique properties [7, 8] . Owing to the strong σ‐donating ability and the high tunability of the side‐groups, manifold applications dealing with the functionalization of surfaces [9–13] and nanoparticles [14–21] have been reported [22–24] .…”

Section: Introductionmentioning

confidence: 99%

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Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

et al. 2022

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Self‐assembly of cyclohexyl cyclic (alkyl)(amino)carbenes (cyCAAC) can be realized and reversibly switched from a close‐packed trimer phase to a chainlike dimer phase, enabled by the ring‐flip of the cyclohexyl wingtip. Multiple methods including scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations identified a distinct isomer (axial or equatorial chair conformer) in each phase, and consequently support the conclusion regarding the determination of molecular surface geometry on the self‐assembly of cyCAAC. Moreover, various substrates such as Ag (111) and Cu (111) are tested to elucidate the importance of cyCAAC‐surface interactions on cyCAAC based nanopatterns. These investigations of patterned surfaces prompted a deep understanding of cyCAAC binding mode, surface geometry and reversible self‐assembly, which are of paramount significance in the areas of catalysis, biosensor design and surface functionalization.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

et al. 2022

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“…The continued interest in the synthesis of novel NHC ligands and investigation into their applications is evident from an increase in the number of literature reports about this class of ligands in recent years [ 256 , 257 ]. Among high records of publications concerning different forms of NHC ligands, a good portion is dedicated to those with tethered anionic chelates.…”

Section: Discussionmentioning

confidence: 99%

Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

2021

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Since the discovery of persistent carbenes by the isolation of 1,3-di-l-adamantylimidazol-2-ylidene by Arduengo and coworkers, we witnessed a fast growth in the design and applications of this class of ligands and their metal complexes. Modular synthesis and ease of electronic and steric adjustability made this class of sigma donors highly popular among chemists. While the nature of the metal-carbon bond in transition metal complexes bearing N-heterocyclic carbenes (NHCs) is predominantly considered to be neutral sigma or dative bonds, the strength of the bond is highly dependent on the energy match between the highest occupied molecular orbital (HOMO) of the NHC ligand and that of the metal ion. Because of their versatility, the coordination chemistry of NHC ligands with was explored with almost all transition metal ions. Other than the transition metals, NHCs are also capable of establishing a chemical bond with the main group elements. The advances in the catalytic applications of the NHC ligands linked with a second tether are discussed. For clarity, more frequently targeted catalytic reactions are considered first. Carbon–carbon coupling reactions, transfer hydrogenation of alkenes and carbonyl compounds, ketone hydrosilylation, and chiral catalysis are among highly popular reactions. Areas where the efficacy of the NHC based catalytic systems were explored to a lesser extent include CO2 reduction, C-H borylation, alkyl amination, and hydroamination reactions. Furthermore, the synthesis and applications of transition metal complexes are covered.

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“…Seit dem bahnbrechenden Bericht von Arduengo et al [1] . haben N‐heterocyclische Carbene (NHC) dank ihrer einzigartigen Eigenschaften [2, 3] als Liganden für p‐Block‐Elemente [4] und Übergangsmetalle [5] erhebliches Interesse in der Katalyse geweckt [6–8] . Aufgrund der starken σ‐Donor Fähigkeit und der flexiblen Ausgestaltung der Seitengruppen wurde über vielfältige Anwendungen im Bereich der Funktionalisierung von Oberflächen [9–13] und Nanopartikeln [14–21] berichtet [22–24] .…”

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Reversible Selbstorganisation eines N‐heterocyclischen Carbens auf Metalloberflächen

et al. 2022

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Cyclohexyl(alkyl)(amino)carbene (cyCAAC) bilden selbstorganisierende Monolagen, die durch den Ring‐Flip der Cyclohexyl‐Seitengruppe reversibel von einer dicht gepackten Trimer‐Phase in eine kettenartige Dimer‐Phase umgeschaltet werden können. Mehrere Methoden, darunter Rastertunnelmikroskopie (STM), Röntgen‐Photoelektronenspektroskopie (XPS) und Dichtefunktionaltheorie (DFT)‐Berechnungen, identifizierten ein eindeutiges Isomer (axiales oder äquatoriales Sesselkonformer) in jeder Phase und stützen somit die Schlussfolgerung hinsichtlich des Einflusses der molekularen Oberflächengeometrie auf die Selbstorganisation von cyCAAC. Darüber hinaus wurden verschiedene Substrate wie Ag(111) und Cu(111) getestet, um die Bedeutung der Wechselwirkungen zwischen cyCAAC und der Oberfläche für die auf cyCAAC basierenden Nanomuster aufzuklären. Die Untersuchungen von gemusterten Oberflächen führten zu einem tieferen Verständnis der cyCAAC‐Bindungsweise, der Oberflächengeometrie und der reversiblen Selbstorganisation, die in den Bereichen Katalyse, Biosensor‐Design und Oberflächenfunktionalisierung von herausragender Bedeutung sind.

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Recent advances in the chemistry and applications of N-heterocyclic carbenes

Cited by 436 publications

References 168 publications

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

Reversible Selbstorganisation eines N‐heterocyclischen Carbens auf Metalloberflächen

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