Synthesis of New Pd II Complexes Containing Thioether−Pyrazole Hemilabile Ligands − Structural Analysis by 1 H and 13 C NMR Spectroscopy and Crystal Structures of [PdCl 2 (bddo)] and [Pd(bddo)](BF 4 ) 2 [bddo = 1,8‐Bis(3,5‐dimethyl‐1‐pyrazolyl)‐3,6‐dithiaoctane]

Treatment of the ligands 1,6‐bis(3,5‐dimethyl‐1‐pyrazolyl)‐2,5‐dithiahexane (bddh), 1,7‐bis(3,5‐dimethyl‐1‐pyrazolyl)‐2,6‐dithiaheptane (bddhp), 1,8‐bis(3,5‐dimethyl‐1‐pyrazolyl)‐3,6‐dithiaoctane (bddo) and 1,9‐bis(3,5‐dimethyl‐1‐pyrazolyl)‐3,7‐dithianonane (bddn) with [PdCl 2 (CH 3 CN) 2 ] produces [PdCl 2 (L)] or [Pd 2 Cl 4 (L)] complexes, depending on the stoichiometry. Treatment of the complexes [PdCl 2 (bddo)] and [PdCl 2 (bddn)] with AgBF 4 gives [Pd(bddo)](BF 4 ) 2 and [Pd(bddn)](BF 4 ) 2 . These Pd II complexes have been characterised by elemental analyses, conductivity measurements, IR and 1 H and 13 C NMR spectroscopy where possible. The X‐ray structures of the complexes [PdCl 2 (bddo)] and [Pd(bddo)](BF 4 ) 2 have been determined. In [PdCl 2 (bddo)] the thioether−pyrazole ligand is coordinated through the azine nitrogen atoms to the metal atom, which completes its coordination with two chloride ions in a trans disposition. In [Pd(bddo)](BF 4 ) 2 the metal atom is tetracoordinated by the two thioether sulfur atoms and the two azine nitrogen atoms of the pyrazole rings. Complexes [PdCl 2 (bddo)] and [PdCl 2 (bddn)] were obtained again when the complexes [Pd(bddo)](BF 4 ) 2 and [Pd(bddn)](BF 4 ) 2 were heated under reflux in a solution of Et 4 NCl in CH 2 Cl 2 /MeOH (1:1). (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)