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

The reactions of PhCb degrees SeNa (Cb degrees = o-C2B10H10), prepared by reductive cleavage of Se-Se bond in (PhCb degrees Se)(2) by NaBH4 in methanol, with Na2PdCl4, MCl2(PR3)(2) and [M2Cl2(mu-Cl)(2)(PR3)(2)] afforded a variety of complexes, viz., [Pd(SeCboPh) Cl] (1), [M(SeCb degrees Ph)(2)(PR3)(2)], [M2Cl2(mu-SeCb degrees Ph)(mu-Cl)(PR3)(2)] (M = Pd, Pt) and [Pd2Cl(SeCb degrees Ph)(mu-Cl)(mu-SeCb degrees Ph)(PEt3)(2)] (7) have been isolated. These complexes were characterized by elemental analyses and NMR (H-1, P-31, Se-77, Pt-195) spectroscopy. The structures of [Pd(SeC-b degrees Ph) (2)(PEt3)(2)] (2), [Pt(SeCb degrees Ph)(2)(PMe2Ph)(2)] (3), [Pd2Cl2(mu-SeCb degrees Ph)(mu-Cl)(PMe2Ph)(2)] (5) and [Pd2Cl (SeCb degrees Ph)(mu-Cl)(mu-SeCb degrees Ph)(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 degrees C gave nano-crystals of Pd17Se15. (C) 2010 Elsevier B.V. All rights reserved.