Article

Oxidative addition of the bismuth-chloride bond: synthesis and structure of trans-[PtCl(PCy3)2{BiCl2}].

Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Chemical Communications (Impact Factor: 6.38). 11/2010; 46(42):7894-6. DOI: 10.1039/c0cc00639d
Source: PubMed

ABSTRACT The synthesis and full characterisation of trans-[PtCl(PCy(3))(2){BiCl(2)}] is reported via the oxidative addition of the bismuth-chloride bond across [Pt(PCy(3))(2)]; this represents the first instance of such an oxidative addition reaction to be undertaken by a bismuth halide bond.

0 Bookmarks
 · 
84 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: The synthesis and characterization of substituted benzimidazolin-2-selones (4c–4d) and -tellone (4i) are reported. Upon reaction with halogens (I2, Br2, and Cl2), these selones and tellone yield dihaloselones/tellone (5c–5i). The reaction of dihaloselones with elemental tellurium/tin/bismuth leads to the formation of selone-coordinated monomeric tellurium tetrahalides, tellurium dibromide (8), tin tetrahalides, and bismuth triiodide adducts (7a–7g), respectively. The structures of the tellurium tetrahalide (7a, 7d, and 7g), tellurium dibromide (8), tin tetrahalide, and bismuth triiodide adducts have been established by single-crystal X-ray analysis. The bismuth triiodide adduct is the first neutral tetrameric structure with selones. The bismuth adduct has been used as a single-source precursor for the synthesis of bismuth selenide (Bi2Se3) nanoparticles, which were characterized by powder XRD patterns. The TEM images show the hexagonal shape of the nanoparticles.
    Berichte der deutschen chemischen Gesellschaft 10/2013; 2013(30). · 2.97 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Around 30 years ago, Razuvaev and co-workers [J. Organomet. Chem.1980, 199, 205] reported a unique organometallic cluster (II) containing a metallocycle-based Ge3Bi2Pt core with the first manifestation of the Bi–Pt bonding. This multimetallic cluster was prepared by introducing the Pt(PPh3)2 moiety into the structure of a [(C6F5)6Ge3Bi2] complex (I). We, in turn, quantum chemically investigated fundamental aspects of the structure, stability, bonding, and reactivity of the model heteroelemental (H2E)3Bi2 complexes and their ML2 (L = PH3)-functionalized derivatives along E = C, Si, Ge, Sn, Pb and M = Ni, Pd, Pt families. The current work aims to assist the further development of synthetical approaches toward these classes of compounds and to afford new insights into the main group element (E, Bi)–transition metal (M) bonding. Our electronic structure calculations were based on relativistic density functional theory in combination with natural bond orbital and electron localization function analyses, and a quantitative energy decomposition analysis. They allowed identification of molecules, dubbed 1,3-dibismuthabicyclo[1.1.1]carbenoidanes, that are composed of two Bi(0) atoms and three carbenoid H2E: units. Functionalization of the (H2E)3Bi2 complexes with ML2 moieties did not represent an oxidative addition, but rather the carbenoid-like insertion of ML2 into the E–Bi bond of a bicyclo[1.1.1]pentane motif which is characteristic of the (H2E)3Bi2 structures. Such an insertion resulted in the formation of the covalently bonded (H2E)3Bi2[ML2] compounds. Our computational analyses suggest that the compounds, comprising silicon atoms as E, possess the best stability and may be the most viable targets for synthesis.
    Organometallics 06/2012; 31(12):4415−4428. · 4.25 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Geometry, electronic structure and bonding energy analysis of the terminal neutral dihalobismuth complexes of nickel, palladium and platinum trans-[X(PMe3)2M(BiX2)] (M=Ni, Pd, Pt; X=Cl, Br, I) were investigated at the BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters of platinum complex trans-[Cl(PMe3)2Pt(BiCl2)] are in excellent agreement with structurally characterized platinum complex trans-[Cl(PCy3)2Pt(BiCl2)]. The variations in the M–Bi bond distances show that the trans effect of halides is relatively greater than the effects of halides bonded to the Bi atom. Hence, the strength of the M–Bi bond decreases on going from X=Cl to X=I in the complexes trans-[X(PMe3)2M(BiX2)]. From the perspective of covalent bonding, however π-symmetry contributions are, in all complexes, significantly smaller than the corresponding σ bonding contribution. Thus, in these complexes, the [BiX2] behaves predominantly as a σ donor. The natural population analysis (NPA) charge distributions indicate the bismuth atom carries a significant positive charge in all cases. The contributions of the electrostatic interactions ΔEelstat are significantly larger in all bismuth complexes (I–IX) than the covalent bonding ΔEorb. The interaction energy increases in the order NiI.
    Computational and Theoretical Chemistry 07/2011; 967(1). · 1.37 Impact Factor