Alkyne Addition and Insertion Reactions of [(Me3Si)3Si]2Ge⋅PMe3

Silylated germylene–PMe₃ adducts exchange their phosphane moiety smoothly for an N‐heterocyclic carbene or isocyanide species to form their respective base adducts. Reaction of the silylated germylene–PMe₃ adducts with monosubstituted alkynes produce germylene adducts with the alkyne inserted into a Ge?Si bond. A computational study of this process provides evidence for the initial formation of a germirene, which rearranges to a vinylgermylene species. The thermodynamic driving force for this reaction is provided by subsequent adduct formation with PMe₃. Reaction of the PMe₃ adduct of bis[(trimethylsilyl)silyl]germylene with disubstituted alkynes leads to the formation of stable germirenes, which can be isomerized further to silagermetes.     

A cyclic disilylated stannylene: synthesis, dimerization, and adduct formation

Reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with [(Me(3)Si)(2)N](2)Sn led to the formation of an endocyclic distannene via the dimerization of a transient stannylene. In the presence of strong donor molecules such as PEt(3), the stannylene could be trapped as adduct. Reaction of the PEt(3) derivative with B(C(6)F(5))(3) gave rise to the formation of the stannylene B(C(6)F(5))(3) adduct.     

Effect of multivalent cations,temperature, and aging on SOM thermal properties

Multivalent cations are suggested to influence the supramolecular structure of soil organic matter (SOM) via inter- and intra-molecular interactions with SOM functional groups. In this study, we tested the combined effect of cations, temperature treatment, and isothermal aging on SOM matrix properties. Samples from a peat and a mineral soil were either enriched with Na, Ca, and Al or desalinated in batch experiments. After treatment at 25, 40, 60, and 105 °C and after different periods of aging at 19 °C and 31 % relative humidity, we investigated the physicochemical matrix stability and the thermal stability against combustion. We hypothesized that multivalent cations stabilize the SOM matrix, that these structures disrupt at elevated temperatures, and that aging leads to an increase in matrix stability. The results show that cation-specific effects on matrix rigidity started to evolve in the peat only after 8 weeks of aging and were significantly lower than the temperature effects. Temperature treatment above 40 °C caused a non (or not immediately) reversible loss of water molecule bridges (WaMB) and above 60 °C a partly reversible melting process probably of semi-crystalline poly(methylene). Thermal stability increased with increasing cation valence and degree of protonation and was much less affected by temperature. Generally, Na-treated and control samples revealed lower thermal stability and lower increase in matrix rigidity with aging than those treated with Ca, Al, and H. We conclude that drying at elevated temperatures (>40 °C) may irreversibly change SOM structure via disruption of labile cross-links and melting of semi-crystalline domains.     

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Photoelektronenspektroskopische untersuchung von tris(trimethylelement(IV)aminen, -phosphinen, -arsinen und -stibinen

The PE spectra of [(CH₃)₃Sn]₃N, [(CH₃)₃E]₃P (E = C, Si, Sn), [(CH₃)₃Si]₃As and [(CH₃)₃E]₃Sb (E = C, S, Ge, Sn) are analyzed. The constant level of the ionization potentials of the n-hybrid orbitals of N, P, As, and Sb, together with changes in the hybridization and interactions with ligand MO's is discussed by qualitative MO investigations.