232599-87-0Relevant academic research and scientific papers
Synthesis, Structure, Theoretical Studies, and Ligand Exchange Reactions of Monomeric, T-Shaped Arylpalladium(II) Halide Complexes with an Additional, Weak Agostic Interaction
Stambuli, James P.,Incarvito, Christopher D.,Buehl, Michael,Hartwig, John F.
, p. 1184 - 1194 (2007/10/03)
A series of monomeric arylpalladium(II) complexes LPd(Ph)X (L = 1-AdP tBu2, PtBu3, or Ph 5FcPtBu2 (Q-phos); X = Br, I, OTf) containing a single phosphine ligand have been prepared. Oxidative addition of aryl bromide or aryl iodide to bis-ligated palladium(0) complexes of bulky, trialkylphosphines or to Pd(dba)2 (dba = dibenzylidene acetone) in the presence of 1 equiv of phosphine produced the corresponding arylpalladium(II) complexes in good yields. In contrast, oxidative addition of phenyl chloride to the bis-ligated palladium(0) complexes did not produce arylpalladium(II) complexes. The oxidative addition of phenyl triflate to PdL2 (L = 1-AdPtBu2, PtBu 3, or Q-phos) also did not form arylpalladium(II) complexes. The reaction of silver triflate with (1-AdPtBu2)Pd(Ph)Br furnished the corresponding arylpalladium(II) triflate in good yield. The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear to be stabilized by a weak agostic interaction of the metal with a ligand C-H bond positioned at the fourth-coordination site of the palladium center. The strength of the Pd...H bond, as assessed by tools of density functional theory, depended upon the donating properties of the ancillary ligands on palladium.
Oxidative Addition of Aryl Sulfonates to Palladium (0) Complexes of Mono- and Bidentate Phosphines. Mild Addition of Aryl Tosylates and the Effects of Anions on Rate and Mechanism
Roy, Amy H.,Hartwig, John F.
, p. 194 - 202 (2008/10/09)
An analysis of the oxidative additions of aryl triflates to palladium(O) complexes of hindered mono and bis(phosphines) and aryl tosylates to palladium(O) complexes of bis(phosphines) are discussed. In the presence added halides reaction of Pd[P(o-tolyl)
Fast palladium catalyzed arylation of alkenes using bulky monodentate phosphorus ligands
Van Strijdonck, Gino P. F.,Boele, Maarten D. K.,Kamer, Paul C. J.,De Vries, Johannes G.,Van Leeuwen, Piet W. N. M.
, p. 1073 - 1076 (2007/10/03)
Complex 1b shows an unprecedented high activity in the Heck reaction. Kinetic studies show that in this system not the oxidative addition but the alkene coordination/migratory insertion is the rate determining step.
