Synthesis of sterically hindered N-benzyladamantyl substituted benzimidazol-2-ylidene palladium complexes and investigation of their catalytic activity in aqueous medium

Dehimat, Zineb Imene; Paşahan, Aziz; Tebbani, Dahmane; Yaşar, Sedat; Özdemır, İsmaıl

doi:10.1016/j.tet.2017.08.037

Cited by 25 publications

(14 citation statements)

References 91 publications

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“…Vinyl imidazole-based salt and NHC-palladium-pyridine complex were prepared according to the methods presented previously. [32][33][34][35][36] The hydrogel-based heterogeneous catalyst was prepared using the free radical polymerization reaction of AAm, AMPS, NHC-Pd-pyridine complex (dichloro[1-(vinyl)-3 -(3, 4, 5-trimethoxybenzyl)-imidazol-2ylidene](pyridine)palladium (II)), and MBA in a DMSO solution. 31 Chemical structure of the prepared poly(AAmco-AMPS)-based NHC-Pd-pyridine catalyst is demonstrated in Figure 1.…”

Section: Preparation Of Vinyl Imidazole-based Salt Nhc-palladium-pyrmentioning

confidence: 99%

The kinetics and mechanism of polymer‐based NHC‐Pd‐pyridine catalyzed heterogeneous Suzuki reaction in aqueous media

Boztepe

Künkül

Gürbüz

et al. 2019

Int J of Chemical Kinetics

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One of the most important challenges of the Suzuki reaction is a green synthesis of reaction products. In terms of economy and ecology, the Suzuki reaction details must be characterized for the industrial‐scale Suzuki reaction processes. In this paper, for the first time, a kinetic and mechanistic study on the Suzuki reaction catalyzed with hydrogel‐supported PEPPSI (pyridine‐enhanced precatalyst preparation stabilization (and) initiation) type NHC‐Pd‐pyridine composite has been investigated. To determine the rate‐limiting step, the effects of reactants and experimental conditions on the heterogeneous Suzuki reaction have been experimentally defined. The experimental results demonstrated that it is possible to reach 100% yield under the optimum reaction conditions, which were found as 75 × 10−3 mol/L of phenylboronic acid (FBA), 50 × 10−3 mol/L of bromoacetophenone (Brac), 125 × 10−3 mol/L of K2CO3, 1 g/L of catalyst, 80°C of reaction temperature, 400 rpm of mixing rate, and 3 h of reaction time. The transmetalation step in the cycle was defined as the rate‐limiting step. On the basis of kinetic results, a mathematical reaction rate expression was presented assuming the steady‐state approach to steps of the catalytic cycle. The activation energy (Ea) of the reaction was estimated to be 34.88 kJ/mol.

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Section: Preparation Of Vinyl Imidazole-based Salt Nhc-palladium-pyrmentioning

confidence: 99%

The kinetics and mechanism of polymer‐based NHC‐Pd‐pyridine catalyzed heterogeneous Suzuki reaction in aqueous media

Boztepe

Künkül

Gürbüz

et al. 2019

Int J of Chemical Kinetics

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“…Numerous ONO, NNN, PCP, PNP and NCN pincer complexes have been reported, which act effectively as catalysts for the coupling reactions, C‐H activation, water splitting, asymmetric transformations, etc . Designing such pincer ligands has drawn enormous attention in the past few years .…”

Section: Introductionmentioning

confidence: 95%

“…Though many chemists have studied the effect of different pincer ligands on the catalytic activity of their complexes, only little attention has been paid to understand the role of ancillary ligand in pincer complexes. Our focus towards this direction has already achieved phosphine‐free Pd(II)‐NNN pincer catalysts for the SMC reaction, where we have found that CH 3 CN can replace PPh 3 ancillary ligand without compromising the activity . Subsequently we have compared the catalytic activity between the pincer complexes containing CH 3 CN ( sp hybridized N) ancillary ligand and those with bulky 2‐bromopyridine ( sp 2 hybridized N), towards the same SMC reaction; the results are being presented in this paper.…”

Section: Introductionmentioning

confidence: 99%

“…[4][5] Numerous ONO, NNN, PCP, PNP and NCN pincer complexes have been reported, which act effectively as catalysts for the coupling reactions, C-H activation, water splitting, asymmetric transformations, etc. [6][7][8][9][10][11][12][13][14][15][16][17][18] Designing such pincer ligands has drawn enormous attention in the past few years. [18] Pd is being regarded as "state of the art" in cross-coupling reactions as a catalyst and also in various organic conversions.…”

Section: Introductionmentioning

confidence: 99%

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Effect of 2‐Bromopyridine Ancillary Ligand in the Catalysis of Pd(II)‐NNN Pincer Complexes towards Suzuki‐Miyaura Cross‐Coupling Reaction

et al. 2019

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Pd(II)‐NNN pincer complexes containing sterically hindered 2‐bromopyridine (sp2 hybridized N donor) as ancillary ligand have been synthesized in order to compare their catalytic efficiency with the reported analogous complexes containing acetonitrile (sp hybridized N donor) ancillary ligand. The complexes have been characterized by analytical and spectroscopic techniques. Single crystal XRD reveals distorted square planar structure of complex 1. These complexes have been investigated as catalysts for the Suzuki‐Miyaura cross‐coupling (SMC) reaction. The scope is extended using various substituted aromatic/aliphatic halides. The activity of the Pd(II)‐NNN pincer complexes bearing bulky 2‐bromopyridine ancillary ligand is not higher compared to that of the complexes with acetonitrile ancillary ligand, which shows superiority of acetonitrile ancillary ligand.

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“…Since the (IPr)Pd(acac)Cl was synthesized in 2005 ( Figure a), NHC‐based palladium catalysts have been developed greatly owing to its excellent catalytic activity in the cross‐coupling reaction. Some groups, for example, Nolan, Organ, Buchwald, and İsmail Özdemir, made great progress in structure design and synthesis methods of bulky NHCs. A series of ligands have been synthesized, such as Pd‐PESSI‐Ipent (Figure b), Pd(ITent)(cin)Cl (Figure c), and so on.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Poly(Bulky N‐Heterocyclic Carbene) as the Self‐Supporting Catalyst toward Suzuki–Miyaura Reaction

Peng

Zhang

Deng

et al. 2018

Macro Chemistry & Physics

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A novel self‐supporting palladium catalyst based on a polymer containing bulky N‐heterocyclic carbene [P(b‐NHC‐Pd)] is prepared successfully by a simple method, and its palladium content reaches 1.35 mmol g−1. Due to the bulky structure of NHC‐PdCl2‐3‐chloropyridine and high content of palladium active sites, this catalyst exhibits excellent catalytic activity for a wide variety of different substrates in Suzuki–Miyaura reaction in air atmosphere. Owing to its heterogeneous performance, the catalyst can be easily separated and reused. After six recycles, the catalytic activity decreases little. Hence, P(b‐NHC‐Pd) could be employed as a recoverable catalyst for cross‐coupling reactions.

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Synthesis of sterically hindered N-benzyladamantyl substituted benzimidazol-2-ylidene palladium complexes and investigation of their catalytic activity in aqueous medium

Cited by 25 publications

References 91 publications

The kinetics and mechanism of polymer‐based NHC‐Pd‐pyridine catalyzed heterogeneous Suzuki reaction in aqueous media

The kinetics and mechanism of polymer‐based NHC‐Pd‐pyridine catalyzed heterogeneous Suzuki reaction in aqueous media

Effect of 2‐Bromopyridine Ancillary Ligand in the Catalysis of Pd(II)‐NNN Pincer Complexes towards Suzuki‐Miyaura Cross‐Coupling Reaction

Preparation of Poly(Bulky N‐Heterocyclic Carbene) as the Self‐Supporting Catalyst toward Suzuki–Miyaura Reaction

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