A theoretical investigation of the oxidation states of palladium complexes and their role in the carbonylation reaction

Bottoni, Andreà; Carvajal, Maria Angels; Miscione, Gian Pietro; Novoa, Juan J.

doi:10.1080/00268976.2010.486139

Cited by 6 publications

(4 citation statements)

References 66 publications

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“…They suggested the following reaction mechanism for the reduction of Pd(OAc) 2 by PPh 3 : The anionic Pd(PPh 3 ) 2 (OAc) − species reacts with organohalides by oxidative addition. The existence and stability of these anionic Pd(0) intermediates [Pd(PPh 3 ) n (OAc)] − ( n = 2, 3) have been investigated experimentally and by theoretical calculations. , …”

Section: Introductionmentioning

confidence: 99%

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Insights into the Active Catalyst Formation from Dinuclear Palladium Acetate in Pd-Catalyzed Coupling Reactions: A DFT Study

Roy

Anoop

2022

J. Phys. Chem. A

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We studied the steps in the formation of active palladium catalyst species from palladium acetate dimer employing density functional theory calculations. We explored the possible pathways with an automated reaction search and studied the kinetics with stochastic simulation analysis. The dimeric form of palladium acetate is considered a resting state of the catalyst. Our reaction search starting from the dimeric form by sequential ligand addition resulted in experimentally observed monomeric species. We analyzed the bonding in the palladium acetate dimer and the role of Pd in the stability of the dimeric species. We implemented the Gillespie stochastic simulation algorithm to gain more insights into multichannel reaction paths and applied it to the degradation pathways. The analysis of the thermodynamic and kinetic data for these degradation pathways suggests that the dimeric form of the catalyst can be a potential catalytic precursor in the palladium acetate-catalyzed coupling reactions under the experimental reaction conditions.

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Section: Introductionmentioning

confidence: 99%

“…The existence and stability of these anionic Pd(0) intermediates [Pd(PPh 3 ) n (OAc)] − (n = 2, 3) have been investigated experimentally 14 and by theoretical calculations. 15,16 Palladium acetate is a versatile catalyst precursor. 17 The actual resting state of palladium acetate is still a matter of debate.…”

Section: ■ Introductionmentioning

confidence: 99%

Insights into the Active Catalyst Formation from Dinuclear Palladium Acetate in Pd-Catalyzed Coupling Reactions: A DFT Study

Roy

Anoop

2022

J. Phys. Chem. A

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“…For all calculations, we used the B3LYP hybrid approach , to density functional theory (DFT), as implemented in the software package Gaussian 09 . This choice of exchange correlation functional was inspired by reports of mechanistic studies on similar Pd-catalyzed reaction systems. − We used the Stuttgart–Dresden effective core potential (ECP) and the corresponding basis set for Pd. The atoms of main-group elements were represented by the all-electron 6-31G(d,p) basis set ( bs1 ) − for optimizations.…”

Section: Computational and Experimental Detailsmentioning

confidence: 99%

Palladium-Catalyzed Hydroxycarbonylation of Pentenoic Acids. Computational and Experimental Studies on the Catalytic Selectivity

et al. 2017

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The palladium-catalyzed conversion of (bio)pentenoic acid isomers (PEAs) occurs with high activity and selectivity to adipic acid (ADA) in the presence of the diphosphine ligand L 2 = 1,2-bis[(di-tert-butyl)phosphinomethyl]benzene (DTBPX) and an acid cocatalyst. Using density functional theory (DFT) calculations, we show that the active catalyst ([L 2 Pd II -H] + ) isomerizes the PEAs to their equilibrium mixture, from which selective carbonylation and hydrolysis results in the ADA product. Hydrolysis is the rate-limiting and also selectivity-determining step, consisting of two parts, hydration and "product release". After the separation of ADA from Pd(0), the product is in a hydrate form. The conversion of this Pd(0) species to the active catalyst occurs quickly with an acid cocatalyst. This conclusion is also supported by the experimental finding that a moderate acidity increases the overall reaction rate. The bulky P substituents in the DTBPX ligand largely prevent chelation of the pending COOH moiety of PEAs, thus allowing the same high regioselectivity as is obtainable with unfunctionalized long-chain alkenes. We also modeled the CO insertion into the chelate complexes and confirmed an increase of more than 50 kJ mol −1 in the barrier for their conversion.

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“…The existence and stability of these anionic Pd(0) intermediates ([Pd(PPh 3 ) n (OAc) 2 ] − ; n = 2,3) have been investigated experimentally 11 and by theoretical calculations. 12,13 Until now, most of the computational studies on resolving the mechanism of Pd(OAc) 2 catalyzed Heck reaction have considered mononuclear Pd(OAc) 2 as the initial catalyst, which might be a reasonable assumption in some reaction conditions. However, palladium acetate dimer as a potential resting state of the active catalyst cannot be ruled out.…”

Section: Introductionmentioning

confidence: 99%

Insights into the active catalyst formation in palladium catalyzed coupling reaction from di-nuclear palladium acetate: A DFT study

Roy

Anoop

2022

Preprint

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We explored the formation of active palladium catalyst species by degradation of Pd-acetate dimer with the addition of phosphine ligands (PH3 and PPh3 ) with an automated reaction search employing Density Functional Theory calculations followed by kinetic studies with stochastic simulation analysis. Our reaction search starting from dimeric form, considered a resting state of the catalyst, produced similar monomeric species by sequential ligand addition as found in the experimental investigation of the active catalytic species in Heck reactions. We analyzed the bonding in the Pd-acetate dimer and the role of Pd in the stability of the dimeric species. We implemented the Gillespie Stochastic Simulation Algorithm and applied it to the degradation reaction path. This algorithm can give more insights into multi-channel reaction paths. The energetics of the degradation path is reasonably achievable in the experimental reaction conditions that make dimeric species a potential catalytic precursor in the Pd-acetate catalyzed coupling reactions.

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A theoretical investigation of the oxidation states of palladium complexes and their role in the carbonylation reaction

Cited by 6 publications

References 66 publications

Insights into the Active Catalyst Formation from Dinuclear Palladium Acetate in Pd-Catalyzed Coupling Reactions: A DFT Study

Insights into the Active Catalyst Formation from Dinuclear Palladium Acetate in Pd-Catalyzed Coupling Reactions: A DFT Study

Palladium-Catalyzed Hydroxycarbonylation of Pentenoic Acids. Computational and Experimental Studies on the Catalytic Selectivity

Insights into the active catalyst formation in palladium catalyzed coupling reaction from di-nuclear palladium acetate: A DFT study

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