We Already Know Everything about Oxidative Addition to Pd(0): Do We?

Rio, Jordan; Liang, Heng; Perrin, Luc; Perego, Luca Alessandro; Grimaud, Laurence; Payard, Pierre‐Adrien

doi:10.1021/acscatal.3c01943

Cited by 8 publications

(7 citation statements)

References 245 publications

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“…Another important point is that the type of the ligand, Pd ligation state, type of the organic substrate, and even the solvent can strongly affect the mechanism, kinetics, and selectivity of OA to metal complexes. 23,28,29,[54][55][56][57][58][59][60][61] Therefore, the relative activity of Pd complexes and nanoparticles in OA depends on the choice of reference ligand. The rate of the OA to Pd complexes bearing some designer ligands may surpass that to Pd NPs.…”

Section: Discussionmentioning

confidence: 99%

“…[19][20][21][22][23][24][25][26][27][28] However, the high level of reaction mechanism complexity still drastically challenges our understanding of OA, even at the level of molecular complexes. 29 Pd NPs have shown remarkable activity in cross-coupling reactions as versatile and practical catalysts. In many studies, the activity was associated with Pd leached into the solution, not with the surface reactions on Pd NPs.…”

Section: Introductionmentioning

confidence: 99%

“…19–28 However, the high level of reaction mechanism complexity still drastically challenges our understanding of OA, even at the level of molecular complexes. 29…”

Section: Introductionmentioning

confidence: 99%

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Computational analysis of R–X oxidative addition to Pd nanoparticles

Polynski,

Vlasova,

Solovev

et al. 2024

Chem. Sci.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Computational analysis of R–X oxidative addition to Pd nanoparticles

Polynski,

Vlasova,

Solovev

et al. 2024

Chem. Sci.

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“…Pd-catalyzed cross-coupling reactions of (hetero)aryl (pseudo)halides are a mainstay of organic synthesis. The catalytic cycles for these transformations begin with oxidative addition at Pd(0) . Because this step is often rate- and/or selectivity-determining, understanding its mechanism is valuable for improving cross-coupling methodology.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Addition of (Hetero)aryl (Pseudo)halides at Palladium(0): Origin and Significance of Divergent Mechanisms

Kania,

Reyes,

Neufeldt

2024

J. Am. Chem. Soc.

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Two limiting mechanisms are possible for oxidative addition of (hetero)aryl (pseudo)halides at Pd(0): a 3-centered concerted and a nucleophilic displacement mechanism. Until now, there has been little understanding about when each mechanism is relevant. Prior investigations to distinguish between these pathways were limited to a few specific combinations of the substrate and ligand. Here, we computationally evaluated over 180 transition structures for oxidative addition in order to determine mechanistic trends based on substrate, ligand(s), and coordination number. Natural abundance 13 C kinetic isotope effects provide experimental results consistent with computational predictions. Key findings include that (1) differences in highest occupied molecular orbital (HOMO) symmetries dictate that, although 12e − PdL is strongly biased toward a 3-centered concerted mechanism, 14e − PdL 2 often prefers a nucleophilic displacement mechanism; (2) ligand electronics and sterics, including ligand bite angle, influence the preferred mechanism of the reaction at PdL 2 ; (3) phenyl triflate always reacts through a displacement mechanism regardless of the catalyst structure due to the stability of a triflate anion and the inability of oxygen to effectively donate electron density to Pd; and (4) the high reactivity of C−X bonds adjacent to nitrogen in pyridine substrates relates to stereoelectronic stabilization of a nucleophilic displacement transition state. This work has implications for controlling rate and selectivity in catalytic couplings, and we demonstrate application of the mechanistic insight toward chemodivergent cross-couplings of bromochloroheteroarenes.

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“…Several mechanisms of reductive elimination/oxidative addition have been discussed in the literature. , The most common model of the mechanism of reductive elimination is direct reductive elimination, in which there is a concerted dissociation of Pd–C and Pd–X bonds and the simultaneous formation of a new C–X chemical bond (Scheme a). Direct reductive elimination usually proceeds via a three-membered cyclic transition state.…”

Section: Introductionmentioning

confidence: 99%

Comparative Study of Pd-Mediated Carbon–Carbon, Carbon–Heteroatom, and Heteroatom–Heteroatom Bond Formation/Breakage (C ═ C_sp³, C_sp², C_sp; X = B, N, O, Si, P, S, Se, Te)

Gordeev,

Musaev,

Ananikov

2023

Organometallics

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center). The relationship between the structural lability of the (R) 2 Pd(L) 2 complexes and the probability of reductive elimination was determined by DFT molecular dynamics. An analysis of the calculated bond formation barriers and reaction energy showed that, in most cases, their values for unsymmetrical RX coupling are intermediate between the values for the reactions of symmetrical RR and XX coupling. The influence of the electronic properties of the coupling groups on the stabilization of the cis form of the complexes, which are suitable pre-reaction complexes for reductive elimination, was shown. The additivity of the energy difference between the cis and trans isomers was established: the cis−trans isomerization energies for the (R)(X)Pd(L) 2 complexes are intermediate between the corresponding energies for the (R) 2 Pd(L) 2 and (X) 2 Pd(L) 2 complexes. A high degree of additivity of the QTAIM charge of the palladium atom in all of the considered complexes was analyzed.In the present detailed study, we establish a hierarchy in bond formation barriers, emphasizing the influence of carbon center types, and discern the impact of coupling groups containing heteroatoms, revealing distinct trends based on carbon center types.

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We Already Know Everything about Oxidative Addition to Pd(0): Do We?

Cited by 8 publications

References 245 publications

Computational analysis of R–X oxidative addition to Pd nanoparticles

Computational analysis of R–X oxidative addition to Pd nanoparticles

Oxidative Addition of (Hetero)aryl (Pseudo)halides at Palladium(0): Origin and Significance of Divergent Mechanisms

Comparative Study of Pd-Mediated Carbon–Carbon, Carbon–Heteroatom, and Heteroatom–Heteroatom Bond Formation/Breakage (C ═ C_sp³, C_sp², C_sp; X = B, N, O, Si, P, S, Se, Te)

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We Already Know Everything about Oxidative Addition to Pd(0): Do We?

Cited by 8 publications

References 245 publications

Computational analysis of R–X oxidative addition to Pd nanoparticles

Computational analysis of R–X oxidative addition to Pd nanoparticles

Oxidative Addition of (Hetero)aryl (Pseudo)halides at Palladium(0): Origin and Significance of Divergent Mechanisms

Comparative Study of Pd-Mediated Carbon–Carbon, Carbon–Heteroatom, and Heteroatom–Heteroatom Bond Formation/Breakage (C ═ Csp3, Csp2, Csp; X = B, N, O, Si, P, S, Se, Te)

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Comparative Study of Pd-Mediated Carbon–Carbon, Carbon–Heteroatom, and Heteroatom–Heteroatom Bond Formation/Breakage (C ═ C_sp³, C_sp², C_sp; X = B, N, O, Si, P, S, Se, Te)