6533b82dfe1ef96bd1291c9f
RESEARCH PRODUCT
A Cation-Captured Palladium(0) Anion: Synthesis, Structure, and Bonding of [PdBr(PPh3)2]− Ligated by an N-Heterocyclic Phosphenium Cation
Zachery HynesNathan D. JonesChristine A. CaputoJacquelyn T. PriceAllison L. BrazeauHeikki M. Tuononensubject
ChemistryStereochemistryOrganic Chemistrychemistry.chemical_elementHalideIonInorganic ChemistryMetalchemistry.chemical_compoundBromidevisual_artPolymer chemistryvisual_art.visual_art_mediumPhysical and Theoretical ChemistryPalladiumdescription
Unsaturated N-heterocyclic phosphenium cations (uNHP) stabilize the [Pd0(PR3)2X]− anion proposed over the past decade to be the crucial but elusive intermediate in palladium-catalyzed cross-coupling reactions (X = halide). Insertion of metal into the P−Br bond of the precursor mesityl-substituted bromophosphine gives the structurally characterized Pd(0)-phosphenium complex (uNHPMes)Pd(PPh3)2Br, which features a long Pd−Br bond (2.7240(9) A) and the shortest known Pd−P bond (2.1166(17) A). The reaction is proposed to proceed by an associative pathway involving a Pd-bromophosphine complex that undergoes P-to-Pd bromide transfer.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2009-08-14 | Organometallics |