Abstract

This work describes the synthesis, characterisation and reactivity of new methylallyl Pd(II) complexes that contain bidentate 2-(methylthio-N-benzylidene)anilines as ligands. The reaction of the binuclear complex [(?3-Me-allyl)Pd(?-Cl)2] with AgBF4 causes the total abstraction of the chloride bridges, with the subsequent formation of an intermediary fragment of Pd(II). This fragment in turn reacts with neutral bidentate 2-(methylthio- N -benzylidene)anilines to give cationic complexes of Pd(II) of general formula [(?3-Me-allyl)Pd(? 2-S,N-MeSC6H4N=CHC6 H4(X)Y)]BF4 [X=H, Y=H (1); X=F, Y=H (2); X=Me, Y=H (3); X=H, Y=Cl (4); X=H, Y=Me2N (5); X=H, Y=NO2 (6)]. The new complexes were characterised by means of elemental analysis, IR, NMR [1H, 19F {1H}, 13C{1H}, 31 P{1H}, Dept, 1H-^{H-COSY, HSQC, HMBC] and mass spectroscopies. The reaction of the Pd(II) complexes with nucleophiles such as NaI, (EtO)2PS2K, KCN, KSCN or NaH lead to the deco-ordination of the bidentate ligands to give dimeric or polymeric complexes of Pd(II). The reactivity pattern observed is discussed by a theoretical analysis based on Fukui functions. © 2003 Elsevier B.V. All rights reserved.}