Syntheses of palladium(II) complexes with thiolate and phosphine ligands. X-ray crystal structures of [Pd(tdt)(PPh3)2] · C2H4Cl2 and [Pd2(Hmp)2(PPh3)Cl2]

By the reactions of Pd 2+ , 1,1-dithiolate [SC 6 H 3 (CH 3 )S 2− , SCH 2 CH 2 S 2− or SCH 2 CH (CH 3 )S 2− ] or thiolate (HOC 6 H 4 S − ) and PR 3 (R = Ph, Et) in MeOH, the complexes [Pd(tdt)(PPh 3 ) 2 ] ( 1 ), [Pd 2 (edt) 2 (PPh 3 ) 2 ] ( 2 ), [Pd 2 (pdt) 2 (PPh 3 ) 2 ] ( 3 ), [Pd 2 (edt) 2 (PEt 3 ) 2 ] ( 4 ), [Pd 2 (pdt) 2 (PEt 3 ) 2 ] ( 5 ), [Pd 2 (Hmp) 2 (PPh 3 ) 2 Cl 2 ] ( 6 ) and [Pd 2 (tdt) 2 (PEt 3 ) 2 ] ( 7 ) (tdt = 1,2-toluenedithiolateedt = 1,2-ethanedithiol, pdt = 1,2-propanedithiol and mp = mercaptophenol) were prepared and analysed by X-ray diffraction. All palladium atoms are tetra-coordinated with distorted square-planar geometry of phosphorus and/or sulfur atoms. The reaction mechanism of Pd 2+ , 1,2-dithiolate and PR 3 (R = Et, Ph) is discussed.