|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|
|Publisher / Ed. Institution :||Wiley|
|License (according to publishing contract) :||Licence according to publishing contract|
|Type of review:||Peer review (Publication)|
|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|
|Appears in Collections:||Publikationen Life Sciences und Facility Management|
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