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

Abstract

The reactions of PhCb oSeNa (Cb o = o-C 2B 10H 10), prepared by reductive cleavage of Se–Se bond in (PhCb oSe) 2 by NaBH 4 in methanol, with Na 2PdCl 4, MCl 2(PR 3) 2 and [M 2Cl 2(μ-Cl) 2(PR 3) 2] afforded a variety of complexes, viz., [Pd(SeCb oPh)Cl] ( 1), [M(SeCb oPh) 2(PR 3) 2], [M 2Cl 2(μ-SeCb oPh)(μ-Cl)(PR 3) 2] (M = Pd, Pt) and [Pd 2Cl(SeCb 0Ph)(μ-Cl)(μ-SeCb oPh)(PEt 3) 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), [Pd 2Cl 2(μ-SeCb oPh)(μ-Cl)(PMe 2Ph) 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(PEt 3) 2] ( 2) in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd 17Se 15.