Title: Pincer-type Heck catalysts and mechanisms based on PdIV intermediates : a computational study
Authors : Blacque, Olivier
Frech, Christian M.
Published in : Chemistry - a European journal
Volume(Issue) : 16
Issue : 5
Pages : 1521
Pages to: 1531
Publisher / Ed. Institution : Wiley
Issue Date: 2010
License (according to publishing contract) : Licence according to publishing contract
Type of review: Peer review (Publication)
Language : English
Subjects : Catalysis; Computer simulation; Kinetics; Molecular structure; Organometallic compounds; Palladium; Stereoisomerism; Stilbenes
Subject (DDC) : 540: Chemistry
Abstract: Pincer-type palladium complexes are among the most active Heck catalysts. Due to their exceptionally high thermal stability and the fact that they contain Pd(II) centers, controversial Pd(II)/Pd(IV) cycles have been often proposed as potential catalytic mechanisms. However, pincer-type Pd(IV) intermediates have never been experimentally observed, and computational studies to support the proposed Pd(II)/Pd(IV) mechanisms with pincer-type catalysts have never been carried out. In this computational study the feasibility of potential catalytic cycles involving Pd(IV) intermediates was explored. Density functional calculations were performed on experimentally applied aminophosphine-, phosphine-, and phosphite-based pincer-type Heck catalysts with styrene and phenyl bromide as substrates and (E)-stilbene as coupling product. The potential-energy surfaces were calculated in dimethylformamide (DMF) as solvent and demonstrate that Pd(II)/Pd(IV) mechanisms are thermally accessible and thus a true alternative to formation of palladium nanoparticles.
Departement: Life Sciences and Facility Management
Publication type: Article in scientific Journal
DOI : 10.1002/chem.200902091
ISSN: 0947-6539
1521-3765
URI: https://digitalcollection.zhaw.ch/handle/11475/10474
Appears in Collections:Publikationen Life Sciences und Facility Management

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