<i>In situ</i> transformations of Pd/NHC complexes with N-heterocyclic carbene ligands of different nature into colloidal Pd nanoparticles

Kostyukovich, Alexander Yu.; Tsedilin, Andrey M.; Sushchenko, Ekaterina D.; Eremin, Dmitry B.; Kashin, Alexey S.; Topchiy, Maxim A.; Asachenko, Andrey F.; Nechaev, Mikhail S.; Ananikov, Valentine P.

doi:10.1039/c8qi01095a

Cited by 20 publications

(21 citation statements)

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“…1 ). 27 , 54 , 58 – 64 In this type of mechanisms, M/NHC complexes serve as precursors or reservoirs of the active metal species. The metal–C NHC framework breaks at the activation stage and it does not participate in the catalytic cycle.…”

Section: State-of-the-art Catalysis By Metal Complexes With Nhc Liganmentioning

confidence: 99%

“… 58 The calculated energy barriers of Ph–NHC coupling is in the range of 17.9–25.1 kcal mol –1 for different NHCs. 64 In many catalytic reactions conducted at 50–100 °C such barriers are readily overpassed and the stability of complexes is determined by thermodynamic factors. Reversibility of the C–NHC coupling was confirmed experimentally on an example of the CH 3 –NHC bond activation catalyzed by palladium nanoparticles.…”

Section: Organometallic Chemistry Behind the H–nhc C–nhc And X–nhc Cmentioning

confidence: 99%

“…For example, DFT calculations of Ph–NHC coupling in (NHC)Pd(Ph)(I)DMF complexes predicted lower Δ E ≠ for the bulky IPr ligand (19.2 kcal mol –1 ) than for the non-bulky IMe ligand (20.9 kcal mol –1 ) owing to the splitting of DMF molecule from the complex with IPr ligand. 64 …”

Section: Organometallic Chemistry Behind the H–nhc C–nhc And X–nhc Cmentioning

confidence: 99%

“…For example, ESI-MS monitoring of various Pd/NHC complexes with IMes, IPr, SIpr and other typical ligands in DMF solution of iodobenzene at 100 °C revealed decomposition of the complexes and facile formation of the Ph–NHC coupling products. 64 H–NHC coupling represents a problem during the activation of M/NHC complexes with hydride donors, e.g. alcohols or aliphatic amines.…”

Section: Rational Catalyst Design For the Tuning Of M/nhc Catalytic Smentioning

confidence: 99%

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The key role of R–NHC coupling (R = C, H, heteroatom) and M–NHC bond cleavage in the evolution of M/NHC complexes and formation of catalytically active species

et al. 2020

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Section: State-of-the-art Catalysis By Metal Complexes With Nhc Liganmentioning

confidence: 99%

Section: Organometallic Chemistry Behind the H–nhc C–nhc And X–nhc Cmentioning

confidence: 99%

Section: Organometallic Chemistry Behind the H–nhc C–nhc And X–nhc Cmentioning

confidence: 99%

Section: Rational Catalyst Design For the Tuning Of M/nhc Catalytic Smentioning

confidence: 99%

See 2 more Smart Citations

The key role of R–NHC coupling (R = C, H, heteroatom) and M–NHC bond cleavage in the evolution of M/NHC complexes and formation of catalytically active species

et al. 2020

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“…For the past two decades, serious effort has been put into the development of N ‐heterocyclic carbene (NHC) metal complexes and a revolution has been achieved, especially in their applications as organometallic catalysts 32–38 . This has been attributed to the ability of NHC ligands to donate σ electrons, which leads to the formation of strong and stable bonds with the metals and prevents formation of inactive palladium black in the catalytic cyclic 34,39,40 .…”

Section: Introductionmentioning

confidence: 99%

Novel and efficient bridged bis(N‐heterocyclic carbene)palladium(II) catalysts for selective carbonylative Suzuki–Miyaura coupling reactions to biaryl ketones and biaryl diketones

Mansour

Fettouhi

Ali

2020

Applied Organom Chemis

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Bridged N,N′‐substituted bisbenzimidazolium bromide salts (L1, L2, and L3) were synthesized and fully characterized. Reactions of palladium acetate with L1, L2, and L3 afforded corresponding new bridged bis(N‐heterocyclic carbene)palladium(II) complexes (C1, C2, and C3) in high yields. The X‐ray structure of complex C1 showed that the Pd(II) ion is bonded to the two carbon atoms of the bis(N‐heterocyclic carbene) and two bromido ligands are in the cis position, resulting in a distorted square planar geometry. The three Pd(NHC)2Br2 complexes C1, C2, and C3 were evaluated in carbonylative Suzuki–Miyaura coupling reactions of aryl boronic acids with aryl halides and displayed high catalytic activity with low catalyst loading. The coupling reactions of aryl bromides were selective towards the carbonylation product at higher carbon monoxide pressure.

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Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

Eremin

Denisova

Kostyukovich

et al. 2019

Chemistry A European J

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In one word, how would you describe your research?Dynamic. How did this research begin?During our work on dynamic processes in Pd/NHC catalytic systems, one of the key techniques we utilized was mass spectrometry.E lectrospray ionization mass spectrometry was applied to understand possible reduction pathways of the studied Pd/NHC complexes. Surprisingly,s everal NHC-free species were detected, unstabilized palladium hydride being one of them. This elusive intermediate caught our attention and we delved into the study of the observed phenomena.What is the most significant result of this study?Formation of palladium complexes, non-stabilized by direct metal bonding with strong NHC ligand, makes av ery important point. Dynamic nature of the catalytic system allows ligand-free ionic palladium complexes to be formed. These ionic species do not agglomerate while being in Pd 0 oxidation state and, notably,t hey can be isolated from the reaction mixture and recycled. What was the inspiration for this cover design?Thinking about an artwork that might describe dynamic nature of the studied system, we wanted to highlight the ease with which the catalytic system can transform. This brought us to the sketch of palladium complexes on as eesaw.I nt he image we created, alternative palladium complexes play together as friends, seesawed easily up and down by the possibility of dynamic transformations.Invited for the cover of this issue are ValentineP .A nanikov and co-workers. The image depicts the dynamic behaviour of a Pd/NHCc atalytic systemw ith easy transition from molecular to ionic complex. Read the fullt ext of the article at

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In situ transformations of Pd/NHC complexes with N-heterocyclic carbene ligands of different nature into colloidal Pd nanoparticles

Abstract: A series of Pd/NHC species undergoes R–NHC coupling reaction forming catalytically active NHC-free complexes and/or colloidal Pd nanoparticles.

Cited by 20 publications

References 51 publications

The key role of R–NHC coupling (R = C, H, heteroatom) and M–NHC bond cleavage in the evolution of M/NHC complexes and formation of catalytically active species

The key role of R–NHC coupling (R = C, H, heteroatom) and M–NHC bond cleavage in the evolution of M/NHC complexes and formation of catalytically active species

Novel and efficient bridged bis(N‐heterocyclic carbene)palladium(II) catalysts for selective carbonylative Suzuki–Miyaura coupling reactions to biaryl ketones and biaryl diketones

Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

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