35Cl Nqr spectroscopy of the [PO2Cl2]− and POCl3 groups in Me(PO2Cl2)2·2D (Me = Mg,Ca, Mn; D = POCl3,CH3COOC2H5,CH3COCH3)

³⁵Cl NQR spectra of dichlorophosphates Me(PO₂Cl₂)₂ · 2D (Me = Mg, Ca, Mn; D = CH₃COOC₂H₅, CH₃COCH₃, POCl₃) are studied in the temperature range 77 ? T (K) ? 305. It is shown that the three compounds with CH₃COOC₂H₅ as donor are isomorphic at 77 K, the crystal structure of Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. The structure of Mg(PO₂Cl₂)_2^?· 2CH₃COCH₃ and of Mg(PO₂Cl₂)₂ · 2POCl₃ probably consists of infinite chains as found for Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. Mg(PO₂Cl₂)₂· 2CH₃COOC₂H₅ shows phase transformations and a complicated dynamical behaviour leading to strong deviations from a Bayertype NQR function v = f(T). The donor capacity of POCl₃ in Mg(PO₂Cl₂)₂· 2POCl₃ is comparable with the donor strength in AsCl₃ · POCl₃ · A d_π-p_π overlap of the P-O bond influences the P-Cl bond.     

Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.     

Hydroxylamido(1-)-O,N-Komplexe des Molybdäns(VI) mit terminalen Oxo-, Sulfido- und Selenido-Liganden Die Kristallstrukturen von [MoO2(C5H10NO)2] und von [MoS2(C5H10NO)2]

Hydroxylamido(1-)-O,N Complexes of Molybdenum(VI) Containing Terminal Oxo, Sulfido, and Selenido Ligands. Crystal Structures of [MoO₂(C₅H₁₀NO)₂] and of [MoS₂(C₅H₁₀NO)₂] Molecular complexes of cis-dioxo-bis(hydroxylamido(1-)-O,N)molybdenum(VI) containing O,N-coordinated, N,N-substituted hydroxylamine ligands react with H₂S in toluene substituting one or both terminal oxo groups yielding cis-oxosulfido- and cis-disulfido-bis (hydroxylamido(1-)-O,N) molybdenum complexes, respectively. With H₂Se the corresponding cis-oxoselenido complexes are formed. The crystal structures of the two title compounds containing piperidine-N-oxide as ligands are described: The cis-disulfido complex crystallizes tetragonal in the space group D—I 4 2 m with four formula units per unit cell; the corresponding cis-dioxo complex crystallizes orthorhombic (D—P 2₁2₁2₁; Z = 4). The ¹H—nmr spectra and the UV-visible absorption spectra are reported.     

Synthesis and Odor of Chiral Partial Structures of Khusimone. Part 1

Khusimone (1), one of the main odor-donating compounds of vetiver oil is subject of the following study on structure/odor relationship. The omittance of the ethano bridge of the tricyclic khusimone leads to a bicyclic system. The stereoselective approach to this degraded structure is described, and the olfactory properties are studied. The key step of the synthesis of the hydrindane nucleus is based on a highly diastereoselective conjugate addition to a chiral oxo-cyclopentene-2-carboxylate.     

Massenspektrometrische Untersuchung aromatischer Halogenide der Summenformel C9H11Cl: Mechanismus der Äthylen-Abspaltung aus dem Ion [M ? Cl]+˙

By investigation of isomeric ²H- and ¹³C-labelled C₉H₁₁ Cl-compounds it has been shown that the ion [M ? Cl]⁺ is transformed mainly to the ion [C₇H₇]⁺ via C₂H₄-elimination from alkyl-substituted tropylium-ions. Phenyl-cyclopropane-cations play only a small part, if at all, in this fragmentation process.