Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Boonseng, Sarote; Roffe, Gavin W.; Targema, Msugh; Spencer, John; Cox, Hazel

doi:10.1016/j.jorganchem.2017.02.040

Cited by 13 publications

(2 citation statements)

References 66 publications

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“…In order to follow the Pd(0)-Pd(II) catalytic cycle, the complex 1 (as pre-catalyst) is to shown by Spencer and co-workers although they have investigated the catalytic pathway for Suzuki coupling reaction [62]. It proves that ligand lability in pincer complexes is very supportive and important for catalytic reaction and strengthens our previously mentioned statement.…”

Section: Dft Analysis For Catalytic Studiessupporting

confidence: 59%

Synthesis, Photophysical Properties and Catalytic Activity of Ƙ3-SCS Pincer Palladium (II) Complex of N,N'-Di-Tert-Butylbenzene-1,3-Dicarbothioamide Supported by DFT Analysis

Das¹,

Kannan²,

Kumar³

et al. 2021

Preprint

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The title complex [PdCl(L)] (1), is obtained from the reaction of SCS pincer ligand HL (where, HL = N,N'-di-tert-butylbenzene-1,3-dicarbothioamide) with lithium tetrachloropalladate (II) in methanol. The compound 1 is characterized by elemental analysis, FTIR, 1H, and 13C-NMR spectroscopy, UV-Vis spectroscopy, powder X-ray diffraction and X-ray crystallographic techniques. At room temperature, 1 emits luminescence light of wavelength 460 nm in the solid state upon excitation by UV light of wavelength 280 nm. The average emission lifetime indicates that, both the ligand and complex emission is fluorescence in nature and involves mainly ligand centers π-π* deexcitation. It also shows good catalytic activity towards Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions of aryl bromides with tert-butyl acrylate and p-tolylboronic acid respectively. For both type of reactions, more than 99% conversion of the substrates is found to occur for electronically activated p-nitro bromobenzene using 1 mol % of 1. Further, modern DFT calculations are performed to decipher the mechanistic insight on the preferable pathways of the Mizoroki-Heck cross-coupling reaction. Stepwise free energy of reactions for various probable reaction pathways suggest that the catalytic route has profound preference for Pd(0)-Pd(II) over Pd(II)-Pd(IV) pathway.<br>

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Section: Dft Analysis For Catalytic Studiessupporting

confidence: 59%

Synthesis, Photophysical Properties and Catalytic Activity of Ƙ3-SCS Pincer Palladium (II) Complex of N,N'-Di-Tert-Butylbenzene-1,3-Dicarbothioamide Supported by DFT Analysis

Das¹,

Kannan²,

Kumar³

et al. 2021

Preprint

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“…To further prove the rationality of the above proposed reaction mechanism, we conducted the density functional theory (DFT) calculations at the ωB97X-D/BSI level using Gaussian 09 software. − BSI denotes that the LANL2DZ basis set is used for the palladium center, and 6-31G* basis sets are used for all the other atoms. − The SMD polarizable continuum model in the dichloroethane (DCE) solvent was employed in the optimization and single-point calculations . For the most possible Path C, we have depicted the free energy profiles as the dearomatization and aromatization cycles in Figures and S14.…”

Section: Resultsmentioning

confidence: 99%

Remote-Group-Assisted Facile Oxidative Arylation of Furans and Pyrroles

et al. 2023

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A mild strategy for oxidative Csp2-H arylation of electron-rich furans and pyrroles has been achieved with the aid of remote carbonyl-containing groups. These groups enable the Pd-catalyzed oxidative Csp2-H arylation of furans to proceed under a warm temperature and O2 atmosphere, while distinctly promoting the yield of such a reaction for pyrroles. Supported by the experimental results and density functional theory calculation, an original concept, i.e., the remote-group-assisted Heck-type pathway, is proposed for these transformations. Moreover, the electron-rich substrates including the arylboronic acids as the arylating reagents were found to be well-tolerated, and the strategy has also been applied to the alternative route for synthesizing the skeleton of S-nitrosoglutathione reductase inhibitors.

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Evaluation of the Transferability of the “Flexible Steric Bulk” Concept from N‐Heterocyclic Carbenes to Planar‐Chiral Phosphinoferrocenes and their Electronic Modification

et al. 2020

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The concept of “flexible steric bulk” is discussed at 2‐phenylvinyl‐1‐phosphinoferrocenes. The introduction of freely rotatable 1'‐silyl groups increases the catalytic productivity within the synthesis of tri‐ortho‐substituted biaryls by Suzuki–Miyaura C,C cross‐coupling reactions, giving higher yields with 1/4 of catalyst concentration than for the non‐silylated derivatives. Electronic modification of the P and the vinyl donor functionalities was investigated by introducing substituents in the para positions of both groups. Therein, electron‐withdrawing phosphines increased the yield from 78 to 91 % for a given biaryl, by changing from a diphenylphosphino to the P(p‐CN‐C6H4)2 unit. Opposite results, obtained from electron‐donating and sterically demanding phosphines, were in accordance with the 1J(31P,77Se) values. However, the electron density of the ferrocenyl backbone, expressed by the redox potential of the first ferrocenyl‐related redox process, cannot be correlated with the donor‐properties at the P atom. Changing from a PPh2‐substituted ferrocene to a (RA)‐1,1'‐binaphthyl‐containing phosphonite, a complex interaction between the axial‐ and the planar‐chiral motifs occurs, resulting a change of the absolute biaryl configuration.

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Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Abstract: Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations. Journal of Organometallic Chemistry, 845. pp. 71-81.

Cited by 13 publications

References 66 publications

Synthesis, Photophysical Properties and Catalytic Activity of Ƙ3-SCS Pincer Palladium (II) Complex of N,N'-Di-Tert-Butylbenzene-1,3-Dicarbothioamide Supported by DFT Analysis

Synthesis, Photophysical Properties and Catalytic Activity of Ƙ3-SCS Pincer Palladium (II) Complex of N,N'-Di-Tert-Butylbenzene-1,3-Dicarbothioamide Supported by DFT Analysis

Remote-Group-Assisted Facile Oxidative Arylation of Furans and Pyrroles

Evaluation of the Transferability of the “Flexible Steric Bulk” Concept from N‐Heterocyclic Carbenes to Planar‐Chiral Phosphinoferrocenes and their Electronic Modification

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