The mechanism of the Wacker process. Corroborative evidence for distal addition of water and palladium

Akermark, Bjoern; Soederberg, Bjoern C. G.; Hall, Steven R.

doi:10.1021/om00155a029

Cited by 30 publications

(11 citation statements)

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“…[28] However, experiments conducted by Akermark, Stille, Bäckvall, and co-workers demonstrated that palladium ligated with substituted or deuterium-labeled alkenes formed products by anti oxypalladation. [29][30][31][32] For example, the addition of CO to the combination of bis[(cis-[D 2 ]ethylene)PdCl 2 ] and H 2 O in a buffered solution of CuCl 2 and NaOAc led to the formation of lactone products, and the configuration of the carbon atoms in the lactone indicated that an anti addition of the oxygen atom and palladium to the ethylene had occurred. [30] In fact, Bäckvall, Siegbahn, and coworkers stated that a hydroxymetal olefin complex is too unreactive to undergo cis migration of an OH ligand to a bound alkene.…”

Section: Catalytic Reactions Involving Alkene Insertion Into Mào Bondsmentioning

confidence: 99%

Migratory Insertion of Alkenes into Metal–Oxygen and Metal–Nitrogen Bonds

Hanley

Hartwig

2013

Angew Chem Int Ed

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The insertion of an unsaturated ligand into a MC or MH bond proceeds through migratory insertion, a fundamental organometallic reaction. Recent literature documents evidence of the migratory insertion of alkenes into an MO and MN bonds for alkene alkoxylation and alkene amination reactions, respectively. Herein we provide an overview of the literature and a perspective on how these recent experiments relate to classic experiments on CO and CN bond formation with alkene complexes of the late transition metals.

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Section: Catalytic Reactions Involving Alkene Insertion Into Mào Bondsmentioning

confidence: 99%

Migratory Insertion of Alkenes into Metal–Oxygen and Metal–Nitrogen Bonds

Hanley

Hartwig

2013

Angew Chem Int Ed

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“…Effects of ligand binding strength and solvents may account for anti nucleophilic attack observed in two noteworthy studies, one by Majima and Kurosawa on [Pd(Cp)(PPh 3 )] + in dichloromethane16e and the other by Åkermark et al. with non‐chelating diolefins 16f. The degree that these influences may alter the course of a reaction has not yet been addressed, however.…”

Section: Early Mechanistic Studiesmentioning

confidence: 99%

The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations

2009

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We present a concise review on the most pertinent investigations that illuminate the complicated and elusive mechanism for the Wacker process, homogeneous olefin oxidation by palladium(II) catalysts. For more than four decades, multitudes of creative and elegant studies detailing the nucleophilic addition and other steps of the Wacker process have appeared contradictory, while in fact modern perspective has shown an intricate and colorful picture of the "textbook" organometallic reaction. A summary and critical analysis of previous studies is of great importance to explain resolved and highlight unresolved questions about this frequently misunderstood reaction.

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“…12 Additional stereochemical studies by other groups also supported the anti addition for the Wacker process. 13,14 Ba ¨ckvall, Akermark and co-workers 15,16 used dideuterio-ethene (cis and trans species) with an excess of LiCl (which forms 2-chloroethanol along with acetaldehyde) to carry out their mechanistic studies. The stereochemistry of hydroxypalladation for the reaction pathway leading to 2-chloroethanol unequivocally showed that the process takes place through an anti mechanism.…”

Section: Mechanistic Studies From Experimentsmentioning

confidence: 99%

Challenges in modelling homogeneous catalysis: new answers from ab initio molecular dynamics to the controversy over the Wacker process

et al. 2014

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We present here a review on the mechanistic studies of the Wacker process stressing the long controversy about the key reaction steps. We give an overview of the previous experimental and theoretical works on the topic. Then we describe the importance of the most recent Ab Initio Molecular Dynamics (AIMD) calculations in modelling organometallic reactivity in water. As a prototypical example of homogeneous catalytic reactions, the Wacker process poses serious challenges to modelling. The adequate description 10 of the multiple role of the water solvent is very difficult by using static quantum chemical approaches including cluster and continuum solvent models. In contrast, such reaction systems are suitable for AIMD, and by combining with rare event sampling techniques, the method provides reaction mechanisms and the corresponding free energy profiles. The review also highlights how AIMD has helped to obtain novel understanding of the mechanism and kinetics of the Wacker process.

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The mechanism of the Wacker process. Corroborative evidence for distal addition of water and palladium

Cited by 30 publications

References 1 publication

Migratory Insertion of Alkenes into Metal–Oxygen and Metal–Nitrogen Bonds

Migratory Insertion of Alkenes into Metal–Oxygen and Metal–Nitrogen Bonds

The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations

Challenges in modelling homogeneous catalysis: new answers from ab initio molecular dynamics to the controversy over the Wacker process

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