Synthesis, structures, DFT calculations, and catalytic application in the direct arylation of five-membered heteroarenes with aryl bromides of novel palladium-N-heterocyclic carbene PEPPSI-type complexes

Sandeli, Abd El-Krim; Khiri-Meribout, Naima; Benzerka, Saida; Boulebd, Houssem; Gürbüz, Nevin; Özdemir, Namık; Özdemır, İsmaıl

doi:10.1039/d1nj03388c

Cited by 20 publications

(9 citation statements)

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“…The structures of palladium complexes were optimized using DFT with the B3LYP hybrid functional, by using a basis set of LanL2DZ, which is very common in palladium complexes calculations. Computations have been performed using the Gaussian 16 program package [ 29 , 30 , 31 , 32 , 33 ].…”

Section: Methodsmentioning

confidence: 99%

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Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination

et al. 2022

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The selective determination of metals in waste solutions is a very important aspect of the industry and environmental protection. Knowledge of the contents and composition of the waste can contribute to design an efficient process separation and recovery of valuable metals. The problematic issue is primarily the correct determination of metals with similar properties such as palladium and platinum. Thus this paper focuses on the development of a selective method that enables Pd(II) determination in the presence of Pt(IV) ions using the azo-dye tropaeolin OO (TR). For this purpose, the process of the metalorganic complex formation and Pd(II) ions determination were studied by using UV–Vis spectrophotometry under different conditions: solvents (water and B-R buffer), pH (2.09–6.09), temperature (20–60 °C), anions and cations concentrations. The formed metalorganic complex between Pd and tropaeolin OO allows for distinguishing Pd(II) ions from both platinum complexes, i.e. Pt(II), Pt(IV). Moreover, the proposed method can be applied to solutions containing both chloride and chlorate ions. The obtained characteristic spectrum with two maxima allows the determination of palladium even in the presence of other cations (Na, K, Mg, Zn, Co, Ni, Al) and changed concentrations of Pt(IV) ions. Furthermore, the developed spectrophotometric method for the Pd(II) ions determination using tropaeolin OO is characterized by high selectivity towards palladium ions.

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Section: Methodsmentioning

confidence: 99%

“…The electronic transitions were calculated by using time-dependent DFT(TD-DFT) with the B3LYP functional and the LanL2DZ basis set. In addition, the electronic spectra were calculated assuming water as a solvent using the CPCM method [ 31 ]. The orbitals and electronic spectra were visualized with GausView5.0.…”

Section: Methodsmentioning

confidence: 99%

Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination

et al. 2022

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“…Several authors reported the TM‐catalyzed C5 direct arylation of furfural ( 1 ) as a particular case in a broader scope of heteroaromatic substrates [48–54] . For instance, in 2005, Fagnou and co‐workers reported one example of a direct arylation of 1 with one equivalent of phenyl bromide catalyzed by Pd(OH) 2 /C, leading to 75 % yield of a mixture 12 : 1 of the 2,5‐ and 2,3‐substitued isomers (Scheme 5a) [53] .…”

Section: Selective Functionalization Of Furfural Derivativesmentioning

confidence: 99%

C−H Activation Based Functionalization of Furfural Derivatives

et al. 2022

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Dedicated to Professor Cesare Gennari on the occasion of his 70th birthday.Furfural and related compounds are building blocks of industrial interest, obtained from raw biomass. Their use as precursors of basic and fine chemicals has gained increasing attention as a green alternative to petroleum-derived compounds. Several works have reported the functionalization of furfurals to obtain a wider range of chemicals, opening up new synthetic possibilities and applications, ranging from biofuels to pharmaceuticals. Among these works, processes based on CÀ H activation are the most attractive ones for their atom economy and the possibility to use non-activated substrates. This minireview summarizes the reported methods of direct CÀ H functionalization of furfurals without prior modification of the redox state of the aldehyde function. In particular, the transition metal catalyzed functionalization of each bond of the heteroaromatic nucleus of these molecules is systematically discussed, as well as examples of CÀ H transformations of the aldehyde function.

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“…The B3LYP 44 method was used to optimize all stable substances and intermediate molecules on the possible reaction path at the LanL2MB 45 calculation level. The geometric configurations of all stable substances and intermediates as shown in Figure 2 (see also the Supporting Information).…”

Section: Table 1 Carboxylation Of Imidazole With Co ...mentioning

confidence: 99%

Base-Mediated Direct Carboxylation of Heteroarenes with CO2

et al. 2022

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The characteristic base medium system synergized from Cs2CO3 and t-BuOK is conducted to the direct carboxylation of imidazoles with CO2 in good yield. And oxygen or thia heterocyclic arenes are of the same carboxylation reactivity with CO2 in the catalysis. Density functional theory shows that in situ construction of t-BuOCs is an endothermic process of 38.31 kJ/mol. t-BuOCs can promote the deprotonation of substrates by forming active C-Cs bond in a rather low energy of HOMO (t-BuOCs)−LUMO (imidazole) of 0.28 eV gap, which favor the electrophilic insertion of CO2 by releasing 94.13 kJ/mol of heat.

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Synthesis, structures, DFT calculations, and catalytic application in the direct arylation of five-membered heteroarenes with aryl bromides of novel palladium-N-heterocyclic carbene PEPPSI-type complexes

Abstract: New series of Pd-catalysts based N-heterocyclic carbene ligand PEPPSI-Type, (PEPPSI = Pyridine Enhanced Precatalyst Preparation Stabilization and Initiation) with the general formula [Pd(II)Br2(NHC)(pyridine)]. were synthesized, and fully characterized by spectroscopic...

Cited by 20 publications

References 65 publications

Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination

Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination

C−H Activation Based Functionalization of Furfural Derivatives

Base-Mediated Direct Carboxylation of Heteroarenes with CO2

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