Synthesis and characterization of cyclometallated palladium(II) dithiolate complexes of the type [Pd(E ∩ C)(C ∩ S)

Abstract

Cyclometallated palladium(II) dithiolate complexes of the type [Pd(E ∩C)(S ∩ S)] (where E ∩ CH N,N′-dimethylbenzylamine, azobenzene, 4-MeOC 6H 4CH  NC 6H 4Me-4, 2-phenylpyridine or tris- o-tolylphosphine; S ∩ S  S 2CNEt 2 or S 2P(OR) 2, R  Et, Pr n, Pr i, Bu n or Bu s) have been synthesized by the reaction of [Pd(E ∩ C)(μ−X)] 2 (XCl, OAc) with sodium or ammonium salts of dithio acids. These complexes were characterized by elemental analysis. IR, NMR ( 1H and 31P) and mass spectral data. Treatment of [Pd(N ∩ C){S 2P(OPr n) 2}] [N ∩ C  NC 5H 4C 6H 4 or N(Ph)NC 6H 4] with anhydrous HCl in diethyl ether afforded [Pd(E ∩ C)(μ−Cl)] 2 and the free dithio acid. When reaction was carried out with triphenylphosphine, a dynamic equilibrium was established between [Pd(N ∩ C){S 2P(OPr n) 2}] and [Pd(PPh 3)( η 1−CN){S 2P(OPr n) 2}]. The crystal structure of [P d{N(Me) 2CH 2C 6 H 4}{S 2P(OPr n) 2}] ( 3) has been determined by X-ray diffraction. The compound exhibits distorted square-planar geometry around palladium atom.