Synthesis, Structural Studies, and Catalytic Application of Palladium Complexes Containing Anilido‐Oxazolinate Ligands

A series of palladium anilido‐oxazolinate complexes 1 – 8 prepared from ligand precursors HNArOxa [ ortho ‐C 6 H 4 (NHAr)(4,4‐dimethyl‐2‐oxazoline) where Ar = 2,4,6‐trimethylphenyl, HNPh TriMe Oxa; 2,6‐diisopropylphenyl, HNPh Di i Pr Oxa; phenyl, HNPh H Oxa; 2‐methoxyphenyl, HNPh OMe Oxa; 2‐methylthiophenyl, HNPh SMe Oxa] is reported. Treatment of HNArOxawith 1.1 equiv. Pd(OAc) 2 afforded palladium(II) acetate complexes (NPh TriMe Oxa)Pd(η 2 ‐OAc) ( 1 ) and (NPh Di i Pr Oxa)Pd(η 2 ‐OAc) ( 2 ) as monomeric complexes, [(NPh H Oxa)Pd(OAc)] 2 ( 3 ) as an anilido‐bridged dinuclear complex, [(NPh OMe Oxa)Pd(OAc)] 2 ( 4 ) as an acetate‐bridged dinuclear complex, and (NPh SMe Oxa)Pd(OAc) ( 5 ) as a monomeric complex. The reactions of 2 , 4 , and 5 with an excess of NaCl (aq.) in acetone yielded palladium(II) chloride complexes, [(NPh Di i Pr Oxa)Pd(Cl)] 2 ( 6 ) as a chloro‐bridged dinuclear complex, (NPh OMe Oxa)Pd(Cl) ( 7 ) as a monomeric complex, [(NPh OMe Oxa)Pd(Cl)] 2 ( 7′ ) as an anilido‐bridged dinuclear complex, and (NPh SMe Oxa)Pd(Cl) ( 8 ) as a monomeric complex. The crystal and molecular structures of 1 – 8 are reported, and their application towards Suzuki and Heck reactions with a wide range of aryl halides has been examined.