Synthese und Eigenschaften der Di‐tert‐butylphosphide [M(PtBu2)2]2 (M = Zn,Hg) und [Cu(PtBu2)]4

Syntheses and Properties of Di‐tert‐butylphosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ The phosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ are accessible from reaction of LiPtBu₂ with ZnI₂, HgCl₂ and CuCl, respectively. [M(PtBu₂)₂]₂ (M = Zn, Hg) are dimers in the solid state. X‐ray structural analyses of these phosphides reveal that [M(PtBu₂)₂]₂ (M = Zn, Hg) contain four‐membered M₂P₂‐rings whereas [Cu(PtBu₂)]₄ features a planar eight‐membered Cu₄P₄‐ring. Degradation reaction of LiPtBu₂(BH₃) in the presence of HgCl₂ results in the dimeric phosphanylborane BH₃ adduct [tBu₂PBH₂(BH₃)]₂. X‐ray quality crystals of [tBu₂PBH₂(BH₃)]₂ (monoclinic, P2₁/n) are obtained from a pentane solution at 6 °C. According to the result of the X‐ray structural analysis, the O₂‐oxidation product of [Hg(PtBu₂)₂]₂, [Hg{OP(O)(tBu)OPtBu₂}(μ‐OPtBu)]₂, features in the solid state structure two five‐membered HgP₂O₂‐rings and a six‐membered Hg₂P₂O₂‐ring. Herein the spiro‐connected Hg atoms are member of one five‐membered and of the six‐membered ring.     

Neue Synthesemethoden, 11. Mitt. α-Alkylthiolierung von cyclischen Ketonen via ihre Enamine

Enamines of cyclic ketones were -alkylthiolated in good yields by simply refluxing them with alkyl 4-methylbenzenethiosulfonates and triethylamine in acetonitrile.

     

Advantages and limitations of combining separation techniques with voltammetry

In this review the combination of voltammetric methods of analysis with separation techniques, such as electrochemical separations, extractive separations, chromatography, electrochromatography, electrophoresis, volatilization and coprecipitation is critically discussed. Based on available publications and their own experience, the authors try to evaluate different separation techniques in view of future developments, paying special attention to extraction methods. For organic analysis, chromatography and electrophoresis with voltammetric detection are considered to be especially attractive while for stripping analysis, major progress is expected to be made in the development of electrodes and electronic equipment. Extraction, coprecipitation and volatilization will be of minor significance.     

Electric quadrupole interactions in Ru-Sc alloys

In TDPAC studies of the electric quadrupole interaction in Ru_xSc_1–x alloys two different electric fieldgradients (EFG) have been observed at the site of⁹⁹Ru: V_zz(I)=12.6·10¹⁷ V/cm² and V_zz(II)=18.9·10₁₇ V/cm². The corresponding relative fractions f(I) and f(II), respectively, vary with the Ru concentration x. For low concentrations x<0.01 most nuclei (f(I)0.8) experience the smaller EFG V_zz(I). At x=0.01, however, the fraction f(I) goes abruptly to zero and V_zz(II) becomes dominant. In view of these results the previous interpretation of V_zz(II) as the EFG of dilute Ru on substitutional Sc sites can no longer be maintained. The Ru-Sc configurations producing these EFG's have not yet been identified. In the intermetallic compound Ru₂Sc the interaction is completely different, in RuSc₃, however, similar values have been observed.     

Structure,insertion electrochemistry,and magnetic properties of a new type of substitutional solid solutions of copper,nickel, and iron hexacyanoferrates/hexacyanocobaltates

Substitutional solid solutions of metal hexacyanometalates in which low-spin iron(III) and cobalt(III) ions populate the carbon-coordinated sites were synthesized and studied by powder diffraction including Rietveld refinement, cyclic voltammetry of immobilized microparticles, diffuse reflection vis-spectrometry, and magnetization techniques. The continuous solid solution series of potassium copper(II), potassium nickel(II), and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] show that the substitution of low-spin iron(III) by cobalt(III) in the hexacyanometalate units more strongly affects the formal potentials of the nitrogen-coordinated copper(II) and high-spin iron(III) ions than those of the remaining low-spin iron(III) ions. In the case of copper(II) and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] the peak currents decrease much more than can be explained by stoichiometry, indicating that the charge propagation is slowed by the substitution of low-spin iron(III) by cobalt(III). The Rietveld refinement of all compounds confirmed the structure initially proposed by Keggin for Prussian blue and contradicts the structure described later by Ludi. The dependencies of lattice parameters on composition exhibit in all series of solid solutions studied similar, although small, deviations from ideality, which correlate with the electrochemical behavior. Finally, a series of solid solutions of the composition KNi(0.5)(II)Cu(0.5)(II)[Fe(III)(CN)(6)](1-x)[Co(III)(CN)(6)](x), where both the nitrogen- and carbon-coordinated metal ions are mixed populated and were synthesized and characterized. These are the first examples of solid solutions of metal hexacyanometalates with four different metal ions, where both the nitrogen- and the carbon-coordinated sites possess a mixed population.     

Synthesis of (R,S)-muscone

Construction of the carbon-skeleton of (R,S)-muscone was achieved by reacting methyllithium with the dianion of cyclopentadecanedione-1,3, itself accessible by hydration of cyclopentadecanediyne-1,3.

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Synthese von (R,S)-Muscon (Kurze Mitteilung) Short communication

Zusammenfassung Die Konstruktion des Kohlenstoffgerüstes von (R,S)-Muscon gelingt durch Reaktion des Dianions von Cyclopentadecandion-1,3, das durch Hydratisierung von Cyclopentadecandiin mit Methyllithium erhältlich ist.

     

Determination of decay constants with a sampling flash apparatus. The triplet state lifetimes of anthracene and pyrene in fluid solutions

A sampling flash apparatus for recording weak transient absorptions in the microsecond range is described. Two methods for the evaluation of first- and second-order rate constants from mixed-order plots are briefly discussed. The concentration dependence of the lifetime of anthracene in its excited triplet state has been investigated in cyclohexane at room temperature. It is assumed that the observed decrease in triplet lifetime with increasing anthracene concentration is due to impurity quenching and not due to triplet excimer formation.     

Zur Möglichkeit der planaren Tetrakoordination von Elementen der IV. Hauptgruppe (C,Si, Ge)

On the Possibility of Planar Tetracoordination of the Fourth Main Group Elements (C, Si, Ge) Semiempirical MO calculations (CNDO/2, EHT) have been used to examine the ability of silicon, carbon, and germanium to form planar tetracoordinated compounds. The calculations have been performed for the tetrahedral ground state structures (T_d – symmetry) as well as for the artificial planar structures (D_4h – symmetry) of the compounds CH₄, SiH₄, GeH₄, and CF₄, SiF₄, GeF₄. A comparison between the tetrahedral and planar species showed, that all planar species are less stable. Furthermore they have larger bond distances and their bonds are stronger polarized. The possibility of the examined compounds to form planar structures increases with growing atomic number of the central atom and with increasing electronegativity of the substituents.     

Gold nanoparticle synthesis in graft copolymer micelles

 An amphiphilic poly(acrylic acid)/polystyrene graft copolymer (PAA-g-PS) has been used to form “nanoreactors” for the synthesis of gold clusters. Such copolymers tend to form stable micelles in non-polar organic solvents where the poly(acrylic acid) chains constitute the core, and the polystyrene chains, the shell. In the present study, the micellar structure of PAA-g-PS in toluene has been demonstrated by dynamic light scattering and transmission electron microscopy (TEM). The subsequent preparation of gold-graft copolymer composites involved the introduction of gold chloride (AuCl₃), either in powder form or previously dissolved in ether, into the micellar cores of the PAA-g-PS in toluene. The gold salt was then reduced by ultraviolet (UV) irradiation of the emulsion, or of dried cast films. TEM and ultraviolet-visible (UV/Vis) spectroscopy were used to characterize the resulting composites. Gold particles of less than 5 nm in diameter were observed in all cases, but the size distribution and the spatial arrangement of the clusters in the cast films were modified when diethyl ether was used to introduce AuCl₃ into the PAA-g-PS micellar cores. This was thought to be due to enhanced nucleation of the gold particles and partial disruption of the micellar cores in the presence of diethyl ether. Received: 21 January 1998 Accepted: 11 June 1998     

Über Ferro- und Ferridoppelsalze mehrbasischer Säuren

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