Catalytic transformation of phenylacetylene mediated by phosphine-free ruthenium alkylidene complexes

Czeluśniak, Izabela; Handzlik, Jarosław; Gierada, Maciej; Szymańska-Buzar, Teresa

doi:10.1016/j.jorganchem.2015.03.025

Cited by 11 publications

(23 citation statements)

References 68 publications

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“…Furthermore, their activity in the cyclooligomerization reactions was suggested as well. Both the ruthenium vinylidene complex and stilbene were recently detected during the experimentally observed transformations of the third‐generation Grubbs catalyst in the presence of phenylacetylene …”

Section: Resultsmentioning

confidence: 96%

“…Decoordination of 1,3‐diphenylpropadiene from 5 is associated with the reaction Gibbs energy of 26 kJ mol −1 and gives the “bare” ruthenium complex [RuCl 2 (H 2 IMes)] 6 . The latter is an unstable 12‐electron species that can coordinate up to three 3‐bromopyridyne molecules (Δ G =−149 kJ mol −1 ), resulting in complex [RuCl 2 (3‐Br‐py) 3 (H 2 IMes)] 7 , recently detected as the product of ruthenium alkylidene decomposition . Alternatively, [RuCl 2 (H 2 IMes)] might bind phenylacetylene to give ruthenium mono‐ or bis(alkyne) complexes (Δ G =−91 and −64 kJ mol −1 , respectively).…”

Section: Resultsmentioning

confidence: 99%

“…Further decoordination of ( E )‐stilbene is an equilibrium reaction (Δ G =4 kJ mol −1 ) leading to the 14‐electron ruthenium vinylidene complex ([RuCl 2 (=C=CHPh)(H 2 IMes)]) 11 . Ruthenium vinylidene complexes are thought to be the active species in dimerization of terminal alkynes . Furthermore, their activity in the cyclooligomerization reactions was suggested as well.…”

Section: Resultsmentioning

confidence: 99%

“…Our recent studies have shown that the degradation of the third‐generation Grubbs catalyst [RuCl 2 (=CHPh)(3‐Br‐py) 2 (H 2 IMes)] ( 1 ) (py=pyridine, H 2 IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolidin‐2‐ylidene) leads to unidentified ruthenium species together with the formation of a tris(3‐bromopyridine) complex of ruthenium in the initial step . The decomposition rate of complex 1 is dramatically increased in the presence of phenylacetylene, compared to the thermal degradation.…”

Section: Introductionmentioning

confidence: 87%

“…The postulated pathway for the dimerization of terminal alkynes proceeds by a metal‐mediated alkyne‐to‐vinylidene isomerization, whereas for the cyclotrimerization process the metallacycle pathway is rather suggested . Although the cyclotrimerization and dimerization pathways are not similar, ruthenium alkylidene complexes were reported by us and other groups as efficient precatalysts for both reactions. However, how the alkylidene ligand transforms into the catalytically active species in the presence of terminal alkynes remains an open question.…”

Section: Introductionmentioning

confidence: 99%

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Terminal‐Alkyne‐Induced Decomposition of a Phosphine‐Free Ruthenium Alkylidene Catalyst

2017

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The transformations of the third‐generation Grubbs catalyst [RuCl2(=CHPh)(3‐Br‐py)2(H2IMes)] (py=pyridine, H2IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolidin‐2‐ylidene) in the presence of a terminal alkyne (phenylacetylene) were studied theoretically. The ruthenium η3‐vinylcarbene complex is the most probable product of the reaction between the 14‐electron ruthenium alkylidene species and phenylacetylene. Its subsequent transformation into the ruthenium vinylidene complex and stilbene, both being experimentally observed earlier, is possible. The former is believed to be the active species catalyzing the dimerization of terminal alkynes. The calculated pathway also predicts the formation of [RuCl2(H2IMes)] species, which might initiate the cyclotrimerization of terminal alkynes or transform into the experimentally detected [RuCl2(3‐Br‐py)3(H2IMes)] complex. An alternative mechanism of the Grubbs catalyst decomposition through an intermediate Ru species having alkylidene and vinylidene ligands in the coordination sphere of ruthenium is also proposed.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Terminal‐Alkyne‐Induced Decomposition of a Phosphine‐Free Ruthenium Alkylidene Catalyst

2017

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Coordination chemistry of H‐spirophosphorane ligands towards pentacarbonylchlororhenium(I) – synthesis, structure and catalytic activity of complexes

Skarżyńska

Siczek

Gawryszewska

et al. 2020

Applied Organom Chemis

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Synthesis of a group of carbonyl rhenium coordination compounds with hydrospirophosphorane ligands was carried out and described. Different symmetrical HP(OCH2CH2NH)2L1, HP(OCH2CMe2NH)2L2, HP(OC6H4NH)2L3, and unsymmetrical ligands HP (OCMe2CMe2O)(OC6H4NH) L4 were found to coordinate to the rhenium center as bidentate P,N donor ligands yielding fac‐[ReCl (CO)3Ln], where n = 1–4. Furthermore, monodentate coordination was also observed in some cases, as was clearly presented in the case of [ReCl(CO)2(L4‐κ2P,N)(L4‐κP)] complex. All of the complexes were characterized using optical spectroscopy. Single‐crystalX‐ray diffraction was also performed in the case of fac‐[ReCl(CO)3L3], fac‐[ReCl(CO)3L4], [Re(CO)2(L2)2]Cl and [ReCl (CO)2(L4‐κ2P,N)(L4‐κP)] samples. Complexes [ReCl(CO)3L3] and [ReCl (CO)3L4], both bearing rings of conjugated double bonds within hydrospirophosphorane ligands, exhibited luminescence. Catalytic properties of rhenium complexes were assessed using the representative fac‐[ReCl (CO)3L2] complex in the dimerization reaction of terminal alkynes. An efficient and selective procedure for synthesis of the E‐enynes was developed. Coupling of (2‐chlorophenyl)acetylene was mediated by [ReCl (CO)3L2]/TBAF system with a 100% conversion rate. Different substituents within aromatic alkynes were tolerated and the resulting products were dependent on the nature of the substituents.

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Formation of active species from ruthenium alkylidene catalysts—an insight from computational perspective

et al. 2019

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Ruthenium alkylidene complexes are commonly used as olefin metathesis catalysts. Initiation of the catalytic process requires formation of a 14-electron active ruthenium species via dissociation of a respective ligand. In the present work, this initiation step has been computationally studied for the Grubbs-type catalysts 3 ), using density functional theory (DFT). Additionally, the extended-transition-state combined with the natural orbitals for the chemical valence (ETS-NOCV) and the interacting quantum atoms (IQA) energy decomposition methods were applied. The computationally determined activity order within both families of the catalysts and the activation parameters are in agreement with reported experimental data. The significance of solvent simulation and the basis set superposition error (BSSE) correction is discussed. ETS-NOCV demonstrates that the bond between the dissociating ligand and the Ru-based fragment is largely ionic followed by the charge delocalizations: σ(Ru-P) and π(Ru-P) and the secondary CH … Cl, CH … π, and CH … HC interactions. In the case of transition state structures, the majority of stabilization stems from London dispersion forces exerted by the efficient CH … Cl, CH … π, and CH … HC interactions. Interestingly, the height of the electronic dissociation barriers is, however, directly connected with the prevalent (unfavourable) changes in the electrostatic and orbital interaction contributions despite the favourable relief in Pauli repulsion and geometry reorganization terms during the activation process. According to the IQA results, the isopropoxy group in the Hoveyda-Grubbs-type catalysts is an efficient donor of intra-molecular interactions which are important for the activity of these catalysts.

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Catalytic transformation of phenylacetylene mediated by phosphine-free ruthenium alkylidene complexes

Cited by 11 publications

References 68 publications

Terminal‐Alkyne‐Induced Decomposition of a Phosphine‐Free Ruthenium Alkylidene Catalyst

Terminal‐Alkyne‐Induced Decomposition of a Phosphine‐Free Ruthenium Alkylidene Catalyst

Coordination chemistry of H‐spirophosphorane ligands towards pentacarbonylchlororhenium(I) – synthesis, structure and catalytic activity of complexes

Formation of active species from ruthenium alkylidene catalysts—an insight from computational perspective

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