Kinetic and Electrochemical Studies of the Oxidative Addition of Demanding Organic Halides to Pd(0): the Efficiency of Polyphosphane Ligands in Low Palladium Loading Cross-Couplings Decrypted
International audience; Oxidative addition (OA) of organic halides to palladium(0) species is a fundamental reaction step which initiates the C–C bond formation catalytic processes typical of Pd(0)/Pd(II) chemistry. The use of structurally congested polyphosphane ligands in palladium-catalyzed C–C bond formation has generated very high turnover numbers (TONs) in topical reactions such as Heck, Suzuki, Sonogashira couplings, and direct sp2C–H functionalization. Herein, the OA of aryl bromides to Pd(0) complexes stabilized by ferrocenylpolyphosphane ligands L1 (tetraphosphane), L2 (triphosphane), and L3 (diphosphane) is considered. The investigation of kinetic constants for the addition of Ph…
Polypyrrole–palladium nanoparticles composite as efficient catalyst for Suzuki–Miyaura coupling
International audience; Synthesis of a new hybrid material (Pd/PPy) composed of polypyrrole globules with uniformly incorporated Pd nanoparticles via direct redox reaction between pyrrole and Pd(NH3)(4)Cl-2 in water has been recently reported (V.A. Zinovyeva, M.A.Vorotyntsev, I. Bezverkhyy, D. Chaumont, J.-C. Hierso, Adv. Funct. Mater. 21 (2011) 1064-1075). In the actual study, this procedure has been extended to synthesize a series of Pd/PPy powders with variable palladium content and morphological parameters. Depending on the monomer-to-oxidant ratio in reaction mixture, average diameters of Pd and PPy particles may change in the ranges of 1.25-1.45 and 27-62 nm, respectively, the Pd conc…
ChemInform Abstract: Palladium-Polypyrrole Nanocomposites Pd@PPy for Direct C-H Functionalization of Pyrroles and Imidazoles with Bromoarenes.
Palladium–polypyrrole nanocomposites (Pd@PPy) with unique combination of high palladium dispersion (nanoparticle size 2.4 nm) and high palladium content (35 wt%) are efficient catalysts for the selective arylation of substituted pyrroles and imidazoles with either activated or deactivated aryl bromides. The performances of the recoverable supported palladium catalyst matches the best performances of homogeneous systems based on Pd(OAc)2 at 0.5–0.2 mol%, and largely overwhelm the classical Pd/C catalyst.
Highly Dispersed Palladium-Polypyrrole Nanocomposites: In-Water Synthesis and Application for Catalytic Arylation of Heteroaromatics by Direct C-H Bond Activation
Pd@PPy hybrid catalytic materials are synthesized in water via redox polymerization reaction of pyrrole with [Pd(NH 3 ) 4 Cl 2 ]. The nanocomposites formed are composed of highly dispersed palladium particles which are either zerovalent or easily reducible, and are embedded in spherical polypyrrole globules. A unique combination of high palladium dispersion (NP size: 2.4 nm) and elevated palladium content (35 wt%) is obtained. The components of these novel nanocomposites are characterized by means of FTIR, XPS, XRD, SEM, and TEM microscopy techniques. The process of formation in solution is also monitored using UV-visible and DLS techniques. The application of these novel hybrid nanomateria…
Electrosynthesis as a powerful method for the generation of catalytic intermediates: efficient isolation of a palladium aryl halide oxidative addition product.
International audience; Polyphosphane ligands of controlled conformation promote highly efficient palladium-catalyzed cross-coupling reactions. Electrosynthesis has been used as a new straightforward method to obtain important intermediates in the search for a better mechanistic understanding. As a proof of concept, the facile synthesis of a phenyl iodopalladium(II) complex (2) was conducted at the electrolysis scale from a readily electrogenerated unstable Pd0 precursor.
Palladium–Polypyrrole Nanocomposites Pd@PPy for Direct C–H Functionalization of Pyrroles and Imidazoles with Bromoarenes
International audience; Palladium–polypyrrole nanocomposites (Pd@PPy) with unique combination of high palladium dispersion (nanoparticle size 2.4 nm) and high palladium content (35 wt%) are efficient catalysts for the selective arylation of substituted pyrroles and imidazoles with either activated or deactivated aryl bromides. The performances of the recoverable supported palladium catalyst matches the best performances of homogeneous systems based on Pd(OAc)2 at 0.5–0.2 mol%, and largely overwhelm the classical Pd/C catalyst.