Einsatz von Hochleistungs-Trennkapillaren in der GC.-EIMS./GC.-CIMS.-Analyse: Eine Möglichkeit zur massenspektrometrischen Doppelbindungscharakterisierung in komplexen Monoalkengemischen

In an attempt to determine position and substitution of double bonds in complex mixtures of straight-chain and branched monoalkenes without actually isolating the constituents, GC.-MS. analysis is performed after in-batch preparation of derivatives of a judiciously chosen type. Cyclic phenylboronates (4,5-substituted 2-phenyl-1,3,2-dioxaborols) are prepared from 1,2-diols which are, in turn, obtained from the original alkenes by treatment with osmium tetroxide. Chemical ionization mass spectrometry (CIMS.) is used in addition to conventional electron impact techniques (EIMS.) in sequential GC./CIMS.- and GC./EIMS.runs, yielding complementary structural information for the single components of the mixture. In order to cope with the potential severity of the separation problem, high-efficiency glass capillary columns were employed throughout. The performance of the system used is demonstrated by a complete double bond analysis of a 35-component mixture of monoalkenes in the C₅ to C₉ range.     

Synthese und Basizität 4-heterosubstituierter. Chinuclidine Chinuclidinreihe, 13. Mitteilung

The preparation of several 4-heterosubstituted quinuclidines and the pK_a values of their hydroperchlorates in water are reported.     

SCF MO LCGO studies on the hydration of ions: The systems H+H2O,Li+H2O,and Na+H2O

The energy surfaces of the systems LiOH ₂ ⁺ and NaOH ₂ ⁺ are studied for a number of different geometries within the SCF MO LCAO framework, using a gaussian basis set to approximate the wavefunction. In the minimum energy geometry of both systems the positive ion is bound to the oxygen atom of the water molecule. The computed binding energies and bond distances are: B ^SCF(LiOH ₂ ⁺ ) = 36.0 kcal/mole, d(LiO) = 3.57 a.u., and B ^SCF(NaOH ₂ ⁺ ) = 25.2 kcal/mole, d(NaO) = 4.23 a.u., resp. The results are compared with those of H₃O⁺ and discussed in view of ion-solvent interaction in aquous solutions.It is a pleasure to thank our technical staff for the careful preparation of the input for the programs and for its enthusiastic and skilful assistance in running the computer.     

Carbonylierung von bis(triphenylphosphin)-platin(II)- und -palladium(II)-komplexen in gegenwart von aminen und α-aminosäureestern

The crystal structure of (C₅H₅)₃Pr·CNC₆H₁₁ was determined from single-crystal X-ray diffraction data. The monoclinic unit cell of dimensions a = 8.298(3), b = 21.66(1), c = 11.943(4) Å, and β = 104.98(3)° contains four molecules in general positions of space group P2₁/c. Each molecule is composed of three C₅H₅ rings in a nearly exact trigonal array, η⁵-bonded to the Pr atom at a distance of 2.53 Å to the centroid of each ring, plus a single CNC₆H₁₁ adduct attached to the Pr atom along the trigonal axis at 2.65 Å. The presence of a CN triple bond in the isonitrile moiety and the nearly linear CNC configuration add credence to the previous proposal that there is a pure donor bond from the isonitrile carbon to the metal atom.