Abstract Polymeric complexes of formula [PdCl (TeAr)] n (I) and [Pd (TeAr) 2] n (II) are readily obtained by the reaction between Na 2 [PdCl 4] and NaTeAr (Ar C 6 H 5, C 6 H 4 OCH 3− 4 and C 6 H 4 OCH 2 CH 3− 4) in ethanol at room temperature. Chemical and far infrared spectral evidences support alternating chloride and tellurol bridges in I and tellurol bridges in II. While the reaction of I (At C 6 H 4 OCH 3− 4) with PPh 3 in stoichiometric amount ...