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

The reactions of PhCboSeNa (Cbo = o-C2B10H10), prepared by reductive cleavage of Se–Se bond in (PhCboSe)2 by NaBH4 in methanol, with Na2PdCl4, MCl2(PR3)2 and [M2Cl2(μ-Cl)2(PR3)2] afforded a variety of complexes, viz., [Pd(SeCboPh)Cl] (1), [M(SeCboPh)2(PR3)2], [M2Cl2(μ-SeCboPh)(μ-Cl)(PR3)2] (M = Pd, Pt) and [Pd2Cl(SeCb0Ph)(μ-Cl)(μ-SeCboPh)(PEt3)2] (7) have been isolated. These complexes were characterized by elemental analyses and NMR (1H, 31P, 77Se, 195Pt) spectroscopy. The structures of [Pd(SeCboPh)2(PEt3)2] (2), [Pt(SeCboPh)2(PMe2Ph)2] (3), [Pd2Cl2(μ-SeCboPh)(μ-Cl)(PMe2Ph)2] (5) and [Pd2Cl(SeCboPh)(μ-Cl)(μ-SeCboPh)(PEt3)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(SeCboPh)2(PEt3)2] (2) in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd17Se15.

The reactions of PhCboSeNa (Cbo = o-C2B10H10), with Na2PdCl4, MCl2(PR3)2 and [M2Cl2(μ-Cl)2(PR3)2] afforded a variety of complexes, viz., [Pd(SeCboPh)Cl], [M(SeCboPh)2(PR3)2], [M2Cl2(μ-SeCboPh)(μ-Cl)(PR3)2] (M = Pd, Pt) and [Pd2Cl(SeCb0Ph)(μ-Cl)(μ-SeCboPh)(PEt3)2]. The latter represents the first example of asymmetric coordination of selenolate ligands in binuclear bis chalcogenolate complexes of palladium and platinum. Thermolysis of [Pd(SeCboPh)2(PEt3)2] in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd17Se15.Figure optionsDownload as PowerPoint slide