Quantum mechanical study of the alkoxide-independent pathway of reductive elimination of C–O from palladium (p-cyanophenyl) neopentoxide complex

Autor:	Ali Morsali, Hamed Chegini, Azar Gharib, Mehran Najafi Ardabili, S. Ali Beyramabadi
Rok vydání:	2014
Předmět:	chemistry.chemical_compound chemistry Computational chemistry Aryl Alkoxide chemistry.chemical_element Density functional theory General Chemistry Activation energy Heterolysis Reductive elimination Catalysis Palladium
Zdroj:	Research on Chemical Intermediates. 41:5389-5398
ISSN:	1568-5675 0922-6168
DOI:	10.1007/s11164-014-1640-7
Popis:	In this study the alkoxide-independent pathway of reductive elimination of C–O from palladium (p-cyanophenyl) neopentoxide complex in THF at 47 °C was investigated theoretically by use of density functional theory and the solvent polarized continuum model. On the basis of experimental results a two-pathway mechanism had been proposed: a concerted process (path a) and a two-step process (path b) initiated by inner-sphere attack of the alkoxide ligand on the ipso-carbon atom of the palladium-bound aryl group (step 1) then Pd–C heterolysis to form p-neopentoxybenzonitrile (step 2). The activation energies of the two pathways were calculated by use of the quantum mechanical approach and compared with each other and with experimental results.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::a75cc3a480dade76d2fef88d095b4e2d https://doi.org/10.1007/s11164-014-1640-7 Zobrazit plný text záznamu Full text from SpringerLink