623167-05-5Relevant articles and documents
Copper(I) thiophenolate in copper N-heterocyclic carbene preparation
Cisnetti, Federico,Lemoine, Pascale,El-Ghozzi, Malika,Avignant, Daniel,Gautier, Arnaud
, p. 5226 - 5229 (2010)
Copper(I) thiophenolate was considered as a copper source for the synthesis of Cu(I)-N-heterocyclic carbenes (Cu(I)-NHCs). It displayed a dual mode of reactivity allowing the synthesis of both thiophenolato-Cu(I)-NHCs via the free carbene in a one-pot procedure starting from imidazolium chlorides and chloro-Cu(I)-NHCs by a salt metathesis reaction starting from chloro-Ag(I)-NHCs.
Tunable iridium catalyst designs with bidentate N-heterocyclic carbene ligands for SABRE hyperpolarization of sterically hindered substrates
Pham, Pierce,Hilty, Christian
, p. 15466 - 15469 (2020/12/25)
A series of bidentate N-heterocyclic carbene (NHC) iridium catalysts, [Ir(κC,N-NHC)H2L2]BPh4, are proposed for SABRE hyperpolarization. The steric and electronic properties of the NHCs are used to tune substrate affinity and thereby SABRE efficiency. The sterically hindered substrates 2,4-diaminopyrimidine and trimethoprim yielded maximum proton NMR signal enhancements of ～300-fold and ～150-fold, respectively.
Cuprophilic interactions in highly luminescent dicopper(i)-NHC-picolyl complexes-fast phosphorescence or TADF?
Nitsch, J?rn,Lacemon, Frederick,Lorbach, Andreas,Eichhorn, Antonius,Cisnetti, Federico,Steffen, Andreas
supporting information, p. 2932 - 2935 (2016/02/19)
This case study on a series of monomeric, dimeric and polymeric CuI chlorido NHC-picolyl complexes shows that cuprophilic interactions can ensure strong spin-orbit coupling for fast (reverse)intersystem-crossing T1 虠 S1 an
Palladium complexes with picolyl functionalized N-heterocyclic carbene ligands and their application in the Mizoroki-Heck reaction
Cao, Changsheng,Sun, Rui,Chen, Qian,Lv, Lanlan,Shi, Yanhui,Pang, Guangsheng
, p. 351 - 358 (2013/07/05)
A series of Pd complexes of picoline-functionalized N-heterocyclic carbenes with different substituents were synthesized. The molecular structures of selected complexes were determined by X-ray diffraction studies, showing a pseudo-square-planar structure with a Pd center surrounded by carbene, pyridine, and two chloride ligands. The influence of the different substituents on the structure and reactivity of the complexes has been studied. The catalytic properties of the complexes were investigated in the Mizoroki-Heck reaction for cross-coupling of bromobenzene with a variety of aryl halides. Their performances varied in these reactions but showed good product regioselectivities.
Synthesis of novel heteroditopic carbene-pyridine palladium(II) chloro vinyl complexes. Comparative reactivity of different palladium vinyl derivatives toward transmetalation with alkynyl stannane
Canovese, Luciano,Visentin, Fabiano,Levi, Carlo,Santo, Claudio
, p. 74 - 77 (2013/07/19)
DeC-activated alkynes such as di-t-butyl-ethyne-dicarboxylate (DTA) or the more reactive dimethyl-ethyne-dicarboxylate (DMA) do not react with palladium(II) chloro methyl complexes bearing heteroditopic carbene-pyridine (C-N) as spectator ligands to give the corresponding vinyl derivatives. In order to prepare this type of derivatives we resorted to a dedicated synthetic protocol based on the displacement of labile pyridine-thioether ligands of vinyl palladium pyridine-thioeter species by the carbene-pyridine ligand of carbene-pyridine silver chloride complexes. However, the novel carbene-pyridine vinyl complexes obtained by such synthetic protocol, if compared with other palladium vinyl species with similar steric requirements, display a markedly reduced reactivity toward transmetalation with ethynyl-stannane.
Cationic gold catalysis with pyridine-tethered Au(III) NHC-carbenes: An experimental and DFT computational study
Muuronen, Mikko,Perea-Buceta, Jesus E.,Nieger, Martin,Patzschke, Michael,Helaja, Juho
experimental part, p. 4320 - 4330 (2012/08/08)
A novel strategy is developed to produce catalytically active cationic Au(III) species by pyridine-tethered NHC complexes. The catalytic properties of two NHC complexes, equipped with distinct pyridine moieties, were studied for two catalytic benchmark reactions, the cycloisomerization of alkynylfurans to isobenzofuranoles and o-alkynylanilines to indoles. Optimal catalytic results were obtained employing a complex tethered with an electron-rich, p-methoxy-substituted pyridine. The catalysis showed high selectivity, yielding clean product conversions, while the catalytic TONs achieved in the studied reactions are well comparable with the ones reported in the literature for silver salt-activated Au(I) NHC carbene catalysts. Computational results at the DFT level support the hypothesis that equilibrating ionic complexes are the plausible catalytically active species. Computational inspection of the energetics and molecular orbital involved in the reaction reveals that the ionic state is more favored in the AuCl3NHC complex equipped with the electron-rich pyridine.
