Oxidative and Reductive Cross-Coupling Reactions Catalyzed by an Anionic “Ligandless” Palladium Complex

Abstract

The anionic complex [NBu4]­[Pd­(DMSO)­Cl3], which can be synthesized on a gram scale in a single step starting from commercially available starting materials, has been shown to be an active catalyst in the Mizoroki–Heck reaction of aryl halides. We present two new catalytic applications of this complex: the base-free oxidative Heck reaction and the reductive homodimerization of aryl halides. This complex outperformed other palladium salts. In the latter reaction, the catalyst loading could be reduced to 0.01 mol %. The scope of the reactions has been explored, demonstrating the potential of the anionic palladium complex in these catalytic transformations.

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

“…Such reaction conditions have commonly been referred to as "ligandless" conditions in other systems. [22][23][24][25][26][27][28] Previously,w ef ound that [PPh 4 ][2]a nd [PPh 4 ] 2 [3] (Scheme 1) could be synthesized by the addition of one and two equivalents of "A gCF 3 "t o1 in the presence of [PPh 4 ]Cl. [29] Thee lectronic properties of 2 and 3 were extensively studied through the use of density functional theory (DFT) calculations,s pectroscopy-oriented configuration interaction (SORCI) calculations,X -ray absorption spectroscopy,a nd cyclic voltammetry.…”

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

“…Given these considerations, we became interested in developing new fluoroalkylation methods with nickel that employed solvent as the only coordinating ligand. Such reaction conditions have commonly been referred to as “ligandless” conditions in other systems [22–28] …”

“…Such reaction conditions have commonly been referred to as "ligandless" conditions in other systems. [22][23][24][25][26][27][28] Previously,w ef ound that [PPh 4 ][2]a nd [PPh 4 ] 2 [3] (Scheme 1) could be synthesized by the addition of one and two equivalents of "AgCF 3 "t o1 in the presence of [PPh 4 ]Cl. [29] Thee lectronic properties of 2 and 3 were extensively studied through the use of density functional theory (DFT) calculations,s pectroscopy-oriented configuration interaction (SORCI) calculations,X -ray absorption spectroscopy,a nd cyclic voltammetry.…”

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents

“…Such reaction conditions have commonly been referred to as "ligandless" conditions in other systems. [22][23][24][25][26][27][28] Previously, we found that [PPh4]2 and [PPh4]23 (Chart 1) could be synthesized by the addition of one and two equivalents of "AgCF3" to 1 in the presence of [PPh4]Cl. 29 The electronic properties of 2 and 3 were extensively studied through the use of density functional theory (DFT) calculations, spectroscopyoriented configuration interaction (SORCI) calculations, X-ray absorption spectroscopy, and cyclic voltammetry.…”