NHC-based pincer ligands: carbenes with a bite

Andrew, Rhiann E.; González‐Sebastián, Lucero; Chaplin, Adrian B.

doi:10.1039/c5dt04429d

Cited by 127 publications

(83 citation statements)

References 102 publications

(65 reference statements)

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“…Apart from the strong σ-donor ability, the great interest for these ligands relies on the robustness that they confer to the resulting complexes, upon coordination onto both early [31] and late transition metals [32–33]. In this regard, the group of Chi employed carbene-based chelates as neutral imine substitutes in an attempt to further improved the stability and the performances of their N···H–C stabilized phosphors (Fig.…”

Section: Reviewmentioning

confidence: 99%

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

Cebrián

Mauro

2018

Beilstein J. Org. Chem.

145

114

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Phosphorescent organometallic compounds based on heavy transition metal complexes (TMCs) are an appealing research topic of enormous current interest. Amongst all different fields in which they found valuable application, development of emitting materials based on TMCs have become crucial for electroluminescent devices such as phosphorescent organic light-emitting diodes (PhOLEDs) and light-emitting electrochemical cells (LEECs). This interest is driven by the fact that luminescent TMCs with long-lived excited state lifetimes are able to efficiently harvest both singlet and triplet electro-generated excitons, thus opening the possibility to achieve theoretically 100% internal quantum efficiency in such devices. In the recent past, various classes of compounds have been reported, possessing a beautiful structural variety that allowed to nicely obtain efficient photo- and electroluminescence with high colour purity in the red, green and blue (RGB) portions of the visible spectrum. In addition, achievement of efficient emission beyond such range towards ultraviolet (UV) and near infrared (NIR) regions was also challenged. By employing TMCs as triplet emitters in OLEDs, remarkably high device performances were demonstrated, with square planar platinum(II) complexes bearing π-conjugated chromophoric ligands playing a key role in such respect. In this contribution, the most recent and promising trends in the field of phosphorescent platinum complexes will be reviewed and discussed. In particular, the importance of proper molecular design that underpins the successful achievement of improved photophysical features and enhanced device performances will be highlighted. Special emphasis will be devoted to those recent systems that have been employed as triplet emitters in efficient PhOLEDs.

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Section: Reviewmentioning

confidence: 99%

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

Cebrián

Mauro

2018

Beilstein J. Org. Chem.

145

114

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“…N‐heterocyclic carbenes (NHCs) are now ubiquitous in organometallic chemistry and catalysis because of their strong coordination ability and tunable character, which facilitates the control of the steric and electronic properties at the metal center . The chelate effect derived from coordination of bis‐NHC ligands results in a stable metal‐ligand platform with easily modulable properties . In this context, it is worth noting that iridium(III) bis‐NHC complexes have been reported as active and selective catalysts for the hydrosilylation of alkynes .…”

Section: Introductionmentioning

confidence: 99%

“…[17,18] The chelate effect derived from coordination of bis-NHC ligands results in a stable metal-ligand platform with easily modulable properties. [19] In this context, it is worth noting that iridium(III) bis-NHC complexes have been reported as active and selective catalysts for the hydrosilylation of alkynes. [20,21] However, it draws attention that examples of CO 2 hydrosilylation catalysts based on iridium(III) bis-NHC species have not been so far reported.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights on the Functionalization of CO₂ with Amines and Hydrosilanes Catalyzed by a Zwitterionic Iridium Carboxylate‐Functionalized Bis‐NHC Catalyst

et al. 2019

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The zwitterionic complex [Cp*IrCl{(MeIm)2CHCOO}] (1) efficiently catalyzes the selective hydrosilylation of CO2 to afford the corresponding silylformate. The best reaction performance has been achieved in acetonitrile at 348 K using HSiMe2Ph. The 1‐catalyzed reaction of pyrrolidine with CO2 and HSiMe2Ph strongly depends on the CO2 pressure. At low concentration of CO2 (1 bar) formation of the corresponding silylcarbamate, by insertion of CO2 into the Si−N bond of the in situ generated silylamine was observed, while at higher pressure (3 bar) the formamide derivative was obtained as major reaction product. The unexpected formation of pyrrolidin‐1‐ium formate as intermediate of the reaction the 1‐catalyzed of CO2 with pyrrolidine and HSiMe2Ph has been observed, and its role in the formation of 1‐formylpyrrolidine rationalized. Moreover, a mechanism for the reaction of CO2 with hydrosilanes, in the presence and in the absence of amines, based on theoretical calculations has been proposed.

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“…New types of ligands have been proposed in recent decades which form efficient catalysts with transition metal ions. These ligands are: N-heterocyclic carbene (NHC) [202,203], pincer-like [204][205][206][207][208], redox-active ligands [209][210][211][212], and scorpionates [213][214][215][216][217][218].…”

Section: Polynuclear Metal Complexes As Catalystsmentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

174

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This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst). Works of recent years (mainly 2010-2016) devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon-hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

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NHC-based pincer ligands: carbenes with a bite

Abstract: In this frontier article we overview the emergence and scope of NHC-based CCC and CNC pincer systems, i.e. complexes containing mer-tridentate ligands bearing two NHC donor groups, comment on their effectiveness in applications, and highlight areas for future development and exploitation.

Cited by 127 publications

References 102 publications

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

Mechanistic Insights on the Functionalization of CO₂ with Amines and Hydrosilanes Catalyzed by a Zwitterionic Iridium Carboxylate‐Functionalized Bis‐NHC Catalyst

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

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NHC-based pincer ligands: carbenes with a bite

Abstract: In this frontier article we overview the emergence and scope of NHC-based CCC and CNC pincer systems, i.e. complexes containing mer-tridentate ligands bearing two NHC donor groups, comment on their effectiveness in applications, and highlight areas for future development and exploitation.

Cited by 127 publications

References 102 publications

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

Mechanistic Insights on the Functionalization of CO2 with Amines and Hydrosilanes Catalyzed by a Zwitterionic Iridium Carboxylate‐Functionalized Bis‐NHC Catalyst

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

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Mechanistic Insights on the Functionalization of CO₂ with Amines and Hydrosilanes Catalyzed by a Zwitterionic Iridium Carboxylate‐Functionalized Bis‐NHC Catalyst