Recent developments in the chemistry of stable doubly bonded germanium compounds

During the last 10 years, several compounds of the type Ge=X (X = C, Ge, N, P, S) have been isolated as monomers. The stabilization of such derivatives, which are generally highly polymerizable, was achieved by using very bulky groups both on the germanium atom and on the heteroelement X. Conjugation (particularly in a few germenes and germaimines) and intramolecular or intermolecular coordination with oxygen or nitrogen, also contributes, in some cases, to the stabilization. The X-ray analyses of such compounds show a significant bond shortening of the double bond (8–10%) relative to the corresponding single bond and a planar or nearly planar germanium. These doubly bonded germanium derivatives are usually thermally stable but must be handled in an inert atmosphere because of their high sensitivity to oxygen and moisture; they are extremely reactive, much more than the corresponding carbon analogues. Nearly quantitative additions on the double bond have been observed with electrophiles and nucleophiles, and various types of cycloadditions also occur. Except in one case, a germylene behavior has not been observed, proving that such compounds retain their structural integrity in solution.     

Phasenbeziehungen und Natriumionenleitung im quasi-binären System Na2SiF6/Na3AlF6

Phase Relations and Sodium Ion Conductivity within the Quasi-binary System Na₂SiF₆/Na₂AIF₆ . The phase diagram of the Na₂SiF₆/Na₃AlF₆ system has been determined by means of x-ray powder diffraction, thermal analysis and conductivity measurements in the sub-solidus region. Na₃AlF₆ accomodates up to 73 mol.-% Na₂SiF₆ maintaining the crystal structure type. The sodium ion conductivity increases by about five orders of magnitude upon doping Na₃AlF₆ with Na₂SiF₆.     

The lead tetraacetate oxidation of bisacylhydrazones of α-diketones: A scope re-assesment

Oxidation of the title compounds yields, besides the reported isoimides 3 and/or the amides 4 , also the imides 5 . The observed product dichotomy is considered as the result of an intramolecular nucleophilic attack on the aroyl group, of the pressumed zwitterionic intermediate 2 , by O or N present in the ambident N-aroylimine site of 2 . The results of AM1 calculations agree with the product studies and both permit the formulation of a set of rules correlating structure and selectivity.     

Surface grating formation and erasing on a-Se films

Surface relief formation at holographic recording on amorphous selenium films was demonstrated and investigated. The presence of this optical phase modulation component is essential for ensuring significant, stable and erasable optical recording in a-Se films at 290–320 K temperatures, where conventional photodarkening was known as insignificant and unstable. Photocrystallization can only be observed in super-exposed a-Se films at the given experimental conditions of hologram recording. Erasing behavior of surface relief gratings under heat treatment was also investigated in order to reveal further details of the mechanism. Photoinduced structural transformations within the amorphous phase, connected to local ordering under the condition of light-induced fluidity, are proposed as an explanation for the relief formation and erasing. The observed reversible optical recording process may be useful for the various optoelectronic applications of photoconductive a-Se layers. Received: 12 June 2000 / Accepted: 6 June 2001 / Published online: 30 August 2001     

Quantum-well states and resonances in thin single-crystal layers of noble metals on W(110) substrates

This paper reports on the first experimental observation of quantum-well states and sp-type resonances in thin single-crystal gold, silver, and copper layers formed on single-crystal W(110) surfaces, which result from spatial localization of Bloch-type electronic wave functions in a quantum well with potential barriers at the vacuum/metal and metal/W(110) interfaces. The quantization of the valence-band electronic structure in Au/W(110), Ag/W(110), and Cu/W(110) systems was studied experimentally using angle-resolved photoelectron spectroscopy.     

Flatness in analytic mappings I. On an announcement of Hironaka

We present a stratification by “normal flatness” associated to an analytic mapping, analogous to Hironaka's classical result for analytic spaces. Our construction is based on a generic normal flatness theorem for mappings, proved using techniques concerning the variation of modules of meromorphically parametrized formal power series [1]. The existence of such a stratification was announced by Hironaka [13], but the other claims made in [13] are false. Counterexamples are also presented here.