Oligosilanylated Silocanes.

A number of mono- and dioligosilanylated silocanes were prepared. Compounds included silocanes with 1-methyl-1-tris(trimethylsilyl)silyl, 1,1-bis[tris(trimethylsilyl)silyl], and 1,1-bis[tris(trimethylsilyl)germyl] substitution pattern as well as two examples where the silocane silicon atom is part of a cyclosilane or oxacyclosilane ring. The mono-tris(trimethylsilyl)silylated compound could be converted to the respective silocanylbis(trimethylsilyl)silanides by reaction with KOBu and in similar reactions the cyclosilanes were transformed to oligosilane-1,3-diides.

Hypercoordinated Oligosilanes Based on Aminotrisphenols.

The hypercoordinated silicon chlorides ClSi[(-OCH)N] () and ClSi[(OCHMeCH)N] () were used for the synthesis of catenated derivatives (MeSi)SiSi[(-OCH)N] (), (MeSi)SiSiMeSiMeSi(SiMe)Si[(-OCH)N] (), and (MeSi)SiSi[(OCHMeCH)N] () in reactions with (MeSi)SiK·THF () or (MeSi)SiK·[18-crown-6] (). It was found that the nature of the (MeSi)SiK solvate determines the product of interaction, resulting in the formation of (MeSi)Si(CH)OSi[(OCHMeCH)N] () or . Compounds obtained were characterized using multinuclear NMR and UV-vis spectroscopy and mass spectrometry.

Tuning the Si-N Interaction in Metalated Oligosilanylsilatranes.

Most known silatrane chemistry is concerned with examples where the attached silatrane substituent atom is that of an element more electronegative than silicon. The current study features silylated silatranes with a range of electropositive elements attached to the silyl group. The resulting compounds show different degrees of electron density on the silatrane-substituted silicon atom.

Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes.

The reaction of the potassium 1,3-trisilanediide MeSi[Si(MeSi)K] with SmI and YbI was found to give the respective disilylated complexes MeSi[Si(MeSi)]Sm·2THF and MeSi[Si(MeSi)]Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((RSi)Ln(THF) (x = 0-3)).

Electron Transfer and Modification of Oligosilanylsilatranes and Related Derivatives.

Several silatranyl -substituted oligosilanes were prepared starting from bis(trimethylsilyl)silatranylsilanide. Electrochemical and theoretical investigations of some oligosilanes revealed that electrooxidation occurs by formation of a short-lived cation radical. This species undergoes structural relaxation to form a pair of conformers, with endo and exo relationships with respect to the Si-N interaction.

Synthesis of indium nanoparticles at ambient temperature; simultaneous phase transfer and ripening.

The synthesis of size-monodispersed indium nanoparticles via an innovative simultaneous phase transfer and ripening method is reported. The formation of nanoparticles occurs in a one-step process instead of well-known two-step phase transfer approaches. The synthesis involves the reduction of InCl with LiBH at ambient temperature and although the reduction occurs at room temperature, fine indium nanoparticles, with a mean diameter of 6.

σ-Bond Electron Delocalization in Oligosilanes as Function of Substitution Pattern, Chain Length, and Spatial Orientation.

Polysilanes are known to exhibit the interesting property of σ-bond electron delocalization. By employing optical spectroscopy (UV-vis), it is possible to judge the degree of delocalization and also differentiate parts of the molecules which are conjugated or not. The current study compares oligosilanes of similar chain length but different substitution pattern.

Wagner-Meerwein-Type Rearrangements of Germapolysilanes - A Stable Ion Study.

The rearrangement of tris(trimethylsilyl)silyltrimethylgermane to give tetrakis(trimethylsilyl)germane was investigated as a typical example for Lewis acid catalyzed Wagner-Meerwein-type rearrangements of polysilanes and polygermasilanes. Direct Si NMR spectroscopic evidence is provided for several cationic intermediates during the reaction. The identity of these species was verified by independent synthesis and NMR characterization, and their transformation was followed by NMR spectroscopy.

Oligosilanylsilatranes.

Oligosilanes with attached silatranyl units were obtained by reactions of potassium oligosilanides with a silatranyl triflate. Interaction between Si and N atoms was observed in the Si NMR spectra (upfield-shifted SiO resonances) and in the solid-state structures (Si-N distances between 2.29 and 2.