Bis(N-substituted oxamate)palladate(ii) complexes as effective catalysts for sustainable Heck carbon–carbon coupling reactions in n-Bu4NBr as the solvent

Abstract

Five bis(oxamato)palladate(II) complexes of the formulae (n-Bu₄N)₂[Pd(4-Fpma)₂] (1), (n-Bu₄N)₂[Pd(4-Clpma)₂] (2), (n-Bu₄N)₂[Pd(4-Brpma)₂] (3), (n-Bu₄N)₂[Pd(4-Brpma)₂]·H₂O (3a), (n-Bu₄N)₂[Pd(4-MeOpma)₂] (4) and (n-Bu₄N)₂[Pd(4-Isopma)₂] (5) (n-Bu₄N⁺ = tetra-n-butylammonium, 4-Fpma = N-4-fluorophenyloxamate, 4-Clpma = N-4-chlorophenyloxamate, 4-Brpma = N-4-bromophenyloxamate, 4-MeOpma = N-4-methoxyphenyloxamate and 4-isopma = N-4-isopropylphenyloxamate) have been easily prepared and characterized by spectroscopic methods and the crystal structures of two of them (3a and 4) have been determined by single crystal X-ray diffraction. Each palladium(II) ion in 3a and 4 is four-coordinate with two oxygen and two nitrogen atoms from two fully deprotonated oxamate ligands building a centrosymmetric square planar PdN₂O₂ surrounding. The values of the Pd–N and Pd–O bond lengths vary in the ranges 2.034(3)–2.043(4) and 1.999(4)–2.013(3) Å, respectively. The reduced bite of the chelating oxamate ligands [81.3(2)–81.7(1) (3a) and 81.61(7)° (4)] is at the origin of the mean distortion of the ideal square environment. The catalytic role of compounds 1–5 as structurally well-defined precatalysts for the Heck-vinylation of a series of aryl iodide/bromide derivatives in n-Bu₄NBr as a benign nonaqueous ionic liquid (i.d. molten salt) has been examined and compared with some commercially available palladium(II/0) complexes. From this study, it appears that the oxamate-containing precatalysts 1–5 are not just ecologically benign, but also highly efficient, easily recoverable and reusable at least eight times without any relevant loss of catalytic activity or leaching from the ionic liquid medium.