Mechanism of the oxidative addition of aryl halides to bis-carbene palladium(0) complexes

Autor:	Anny Jutand, Julien Pytkowicz, Sylvain Roland, Pierre Mangeney
Rok vydání:	2010
Předmět:	General Chemical Engineering Aryl chemistry.chemical_element General Chemistry Associative substitution Photochemistry Medicinal chemistry Oxidative addition Catalysis chemistry.chemical_compound Reaction rate constant chemistry Reactivity (chemistry) Carbene Palladium
Zdroj:	Pure and Applied Chemistry. 82:1393-1402
ISSN:	1365-3075 0033-4545
Popis:	Bis-N-heterocyclic carbenes Pd0 complexes, Pd0(NHC)2, are efficient catalysts in Heck reactions performed with aryl bromides or chlorides. The Pd0(NHC)2 that are not stable are generated in situ from PdII precursors PdY2(NHC)2 (Y = halides) after a chemical reduction. The latter procedure can be mimicked by an electrochemical reduction. The transient Pd0(NHCBn)2 is generated by electrochemical reduction of PdY2(NHCBn)2, and its reactivity in oxidative addition to aryl bromides and chlorides is characterized by the same electrochemical technique with the determination of the rate constants. Pd0(NHCBn)2 is found to be more reactive than the mixed complex Pd0(NHCBn)(PPh3). Both are the reactive species in an associative mechanism. Comparison with the isolated Pd0(NHCtBu)2 reveals that Pd0(NHCBn)2 is more reactive than Pd0(NHCtBu)2 even if the latter reacts via the mono-carbene Pd0(NHCtBu) in a dissociative mechanism. This suggests that the formation of mono-carbene Pd0(NHC) is not a guarantee for a fast oxidative addition because it is always generated at low concentration in its equilibrium with the related nonreactive bis-carbene Pd0(NHC)2.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::dfea590f7004935797e3845264b8e338 https://doi.org/10.1351/pac-con-09-09-22 Zobrazit plný text záznamu Plný text ve formátu PDF