Convenient One-Pot Synthesis of L₂Pd(0) Complexes for Cross-Coupling Catalysis

Abstract

A convenient one-pot synthesis of (tBu 3 P) 2 Pd(0) was successfully carried out by using various air-stable Pd(II) salts, such as Pd(cod)Cl 2 , Pd(nbd)Cl 2 , Pd(CH 3 CN) 2 Cl 2 , or Pd(PhCN) 2 Cl 2 , without the use of an external reducing agent. Using Pd(cod)Cl 2 as the precursor, large-scale synthesis of (tBu 3 P) 2 Pd(0) was accomplished in excellent yield and purity. Another protocol was also developed for L 2 Pd(0) complexes via an atom economical one-pot method by reacting in situ generated LPd(R-allyl)Cl complexes (L = tBu 3 P, Cy 3 P, (o-Tol) 3 P, CataXCium A,

Synthesis and catalytic properties of palladium(ii) complexes with P,π-chelating ferrocene phosphinoallyl ligands and their non-tethered analogues

“…30 More recent reports demonstrated that similar Pd( ii )-to-Pd(0) transformations are also possible with the more stable and easier-to-access [PdL(Cl)(η 3 -allyl)] complexes (allyl = various π-coordinated allyl ligands, including cyclic ones, L = phosphine or NHC ligands). 31…”

Aqueous Micelles as Solvent, Ligand, and Reaction Promoter in Catalysis

“…The nature of the ligand or capping agent on the metal particles affects the process cost. Traditionally, Pd nanoparticle-catalyzed reactions used phosphine or nitrogen-based ligands. − However, the use of ligands can be avoided if the amphiphile PS-750-M has a greater tendency to bind to the metal through carbonyl groups. Nevertheless, carrying out ligand-free nanocatalysis can be challenging as nanoparticle agglomerates, which can lead to poor activity.…”

Alkene-Coordinated Palladium(0) Cross-Coupling Precatalysts: Comparing Oxidative Addition and Catalytic Reactivity for Dimethyl Fumarate and Maleic Anhydride Stabilizing Ligands

“…This is either achieved through reduction of a Pd(II) precursor, or by directly using a Pd(0) precursor. There are many prior examples of Pd(II) sources and precatalysts, whereas Pd(0) precursors are less common. − Key examples of Pd(0) sources for cross-coupling catalysis include Pd 2 dba 3 (and its crystalline solvates) for in situ generation, ,,− and homoleptic Pd(PR 3 ) n complexes, including Pd(PPh 3 ) 4 , as single-component catalysts (Figure A). , …”