1-Selenolato-2-phenyl-o-carborane complexes of palladium(II) and platinum(II): Synthesis, spectroscopy and structures

Article abstract of DOI:10.1016/j.jorganchem.2010.08.022

The reactions of PhCb^oSeNa (Cb^o = o-C ₂B₁₀H₁₀), prepared by reductive cleavage of Se-Se bond in (PhCb^oSe)₂ by NaBH₄ in methanol, with Na₂PdCl₄, MCl₂(PR₃)₂ and [M₂Cl₂(μ-Cl)₂(PR₃) ₂] afforded a variety of complexes, viz., [Pd(SeCb^oPh)Cl] (1), [M(SeCb^oPh)₂(PR₃)₂], [M ₂Cl₂(μ-SeCb^oPh)(μ-Cl)(PR ₃)₂] (M = Pd, Pt) and [Pd₂Cl(SeCb ⁰Ph)(μ-Cl)(μ-SeCb^oPh)(PEt₃)₂] (7) have been isolated. These complexes were characterized by elemental analyses and NMR (¹H, ³¹P, ⁷⁷Se, ¹⁹⁵Pt) spectroscopy. The structures of [Pd(SeCb^oPh)₂(PEt ₃)₂] (2), [Pt(SeCb^oPh)₂(PMe ₂Ph)₂] (3), [Pd₂Cl₂(μ-SeCb ^oPh)(μ-Cl)(PMe₂Ph)₂] (5) and [Pd ₂Cl(SeCb^oPh)(μ-Cl)(μ-SeCb^oPh)(PEt ₃)₂] (7) were established by X-ray crystallography. The latter represents the first example of asymmetric coordination of selenolate ligands in binuclear bis chalcogenolate complexes of palladium and platinum. Thermolysis of [Pd(SeCb^oPh)₂(PEt₃)₂] (2) in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd ₁₇Se₁₅.