Palladium complexes with hydrophosphorane ligands (HP∼O and HP∼N), catalysts for Heck cross-coupling reactions

Crystal structure of bis(μ 2-chlorido)-bis(di-p-tolylhydroxyphosphine-κP)-bis(di-p-tolylphosphite-κP)dipalladium(II), C56H58Cl2O4P4Pd2

“…Palladium catalysts, more speci cally those containing phosphine ligands have been intensively studied in homogeneous catalytic reactions such as the Heck and Suzuki cross coupling reaction [1][2][3][4][5][6]. The title compound forms part of an ongoing research study on the synthesis of highly selective and air stable phosphine ligands coordinated to platinum and palladium to ensure minimal by-product formation and to strengthen catalyst stability.…”

Isolation of chloro-bridged arylpalladium complexes, [Pd2Ar2(μ-Cl)2(PR3)2], in palladium catalyzed C–C cross coupling reaction of triarylbismuth with arylhalides

“…These tricoordinated palladium(II) complexes have also been used as a catalyst for polymerization of norbornenes [14] and reactions of arylhalides with organometallic species [15] and amines [16]. Recently binuclear chloro-bridged complexes, [Pd 2 Cl 2 (m-Cl) 2 (PR 3 ) 2 ] have been used as a catalyst in Heck [17] and SuzukieMiyaura [18] cross coupling reactions. In SuzukieMiyaura cross coupling, the reaction between p-bromoanisole and ArB(OH) 2 (Ar ¼ Ph or 4-MeC 6 H 4 ) in the presence of [Pd 2 Cl 2 (m-Cl) 2 (PPh 3 ) 2 ] gives 32 and 46% yields, respectively of the crossed-coupled product [18].…”

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex

“…1 disappeared and a new broad signal at δ =80 ppm appeared. This could be attributed to the Pd dimer (Scheme ) …”

“…Our spectroscopic studies indicated that the dealkylation of the H‐spirophosphorane ligand is possible and leads to a phosphonate moiety that could coordinate easily to the Pd centre. Similar phosphonate complexes catalyzed the Heck coupling and methoxycarbonylation reactions and they might also contribute to the carbonylative Suzuki coupling. In summary, the studied cocktail‐type system contained different forms of Pd and P ligands that contribute to the efficient catalytic process.…”

“…Pd complexes with HSPs have been applied as efficient and regioselective catalysts in Heck and Hiyama cross‐coupling reactions. It emerged that the presence of the spirophosphorane ligand in the coordination sphere of Pd is essential, and the structure of the complex plays a significant role in the catalytic process . It was demonstrated that the kind of HSP ligand coordinated to Pd influences the selectivity of the arylation of n ‐butyl acrylate and the yield of substituted stilbenes in the coupling reaction of aryl halides with substituted styrenes and styrylsilanes.…”