Synthesis, spectroscopy and structures of palladium(II) and platinum(II) complexes containing mercapto- o-carborane

Abstract

The reactions of [M 2Cl 2(μ-Cl) 2(PMe 2Ph) 2] with mercapto- o-carboranes in the presence of pyridine afforded mono-nuclear complexes of composition, [MCl(SCb°R)(py)(PMe 2Ph)] (M = Pd or Pt; Cb° = o-C 2B 10H 10; R = H or Ph). The treatment of [PdCl 2(PEt 3) 2] with PhCb°SH yielded trans-[Pd(SCb°Ph) 2(PEt 3) 2] ( 4) which when left in solution in the presence of pyridine gave another substitution product, [Pd(SCb°Ph) 2(py)(PEt 3)] ( 5). The structures of [PdCl(SCb°Ph)(py)(PMe 2Ph)] ( 1), [Pd(SCb°Ph) 2(PEt 3) 2] ( 4) and [Pd(SCb oPh) 2(py)(PEt 3)] ( 5) were established unambiguously by X-ray crystallography. The palladium atom in these complexes adopts a distorted square-planar configuration with neutral donor atoms occupying the trans positions. Thermolysis of [PdCl(SCb°)(py)(PMe 2Ph)] ( 2) in TOPO (trioctylphosphine oxide) at 200 °C gave nanocrystals of TOPO capped Pd 4S which were characterized by XRD pattern and SEM.