Popp Brian V, Stahl Shannon S
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
J Am Chem Soc. 2006 Mar 8;128(9):2804-5. doi: 10.1021/ja057753b.
The first example of associative displacement of dioxygen from a peroxopalladium(II) complex is reported. Electron-deficient alkenes, p-X-trans-beta-nitrostyrene (X = OCH3, CH3, H, F, Br, CF3, NO2), react quantitatively with (bc)Pd(eta2-O2) (bc = bathocuproine) in dichloromethane at room temperature to form the corresponding palladium(0)-alkene complexes. Mechanistic studies indicate that ligand substitution proceeds through an associative mechanism, and the electronic characteristics of the reactions are consistent with an "oxidatively induced" reductive elimination pathway.
