Theoretical evidence for low-ligated palladium(0): [Pd-L] as the active species in oxidative addition reactions
2006 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 25, no 8, 2066-2073 p.Article in journal (Refereed) Published
The oxidative addition of PhI to Pd-O has been studied by DFT with a continuum representation of the solvent. It is shown that the preferred number of ligands on palladium is lower than would be expected from "conventional wisdom" and the 18-electron rule. The most favored oxidative addition is obtained when Pd is coordinated by only the aryl iodide and one additional ligand in a linear arrangement. The calculations indicate that p-orbitals on the central metal are not involved in bonding in any of the complexes described herein, in good agreement with classic ligand field theory and also with a recent bonding analysis by Weinhold and Landis, but in apparent violation of the 18-electron rule.
Place, publisher, year, edition, pages
2006. Vol. 25, no 8, 2066-2073 p.
Addition reactions, Chemical bonds, Oxidation, Probability density function
IdentifiersURN: urn:nbn:se:kth:diva-48882DOI: 10.1021/om060126qISI: 000236700400032OAI: oai:DiVA.org:kth-48882DiVA: diva2:488414
QC 201202022012-02-012011-11-232012-02-02Bibliographically approved