Synthesis, Characterization, and Catalytic Applications of Palladacyclic Complexes Bearing C,N,S‐Donor Ligands

Abstract

Abstract The preparations of novel tridentate C,N,S‐donor ligand precursors, PhN=C(CMe 2 )(NPh)C=N(CH 2 ) 2 SR [R = CMe 3 ( 2 ); R = Ph ( 3 )] are described. Treatment of 2 and 3 with 1 equiv. of Pd(OAc) 2 affords the orthometallated palladium(II) complexes [PhN=C(CMe 2 )(N‐η 1 ‐Ph)C=N(CH 2 ) 2 SR]Pd(OAc) [R = CMe 3 ( 4 ); R = Ph ( 5 )]. Reaction of 4 and 5 with an excess of LiCl in methanol affords the orthometallated palladium(II) complexes [PhN=C(CMe 2 )(N‐η 1 ‐Ph)C=N(CH 2 ) 2 SR]PdCl [R = CMe 3 ( 6 ); R = Ph ( 7 )]. Crystal structures are reported for compounds 3 and 4 . The application of these novel palladacyclic complexes as catalyses for the Suzuki and Heck reactions with aryl halide substrates was examined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)