Selective synthesis of germasila-adamantanes through germanium-silicon shift processes.

The regioselective synthesis of germasila-adamantanes with the germanium atoms in the bridgehead positions is described starting from cyclic precursors by a cationic sila-Wagner-Meerwein (SWM) rearrangement reaction. The SWM rearrangement allows also a deliberate shift of germanium atoms from the periphery and within the cage structures into the bridgehead positions. This opens the possibility for a synthesis of germasila-adamantanes of defined germanium content and controlled regiochemistry. In the same way that sila-adamantane can be regarded as a molecular building block of elemental silicon, the germasila-adamantane molecules represent cutouts of silicon/germanium alloys.

Electrical and Structural Properties of Si1-xGex Nanowires Prepared from a Single-Source Precursor.

Si1-xGex nanowires (NWs) were prepared by gold-supported chemical vapor deposition (CVD) using a single-source precursor with preformed Si-Ge bonds. Besides the tamed reactivity of the precursor, the approach reduces the process parameters associated with the control of decomposition characteristics and the dosing of individual precursors. The group IV alloy NWs are single crystalline with a constant diameter along their axis. During the wire growth by low pressure CVD, an Au-containing surface layer on the NWs forms by surface diffusion from the substrate, which can be removed by a combination of oxidation and etching. The electrical properties of the Si1-xGex/Au core-shell NWs are compared to the Si1-xGex NWs after Au removal. Core-shell NWs show signatures of metal-like behavior, while the purely semiconducting NWs reveal typical signatures of intrinsic Si1-xGex. The synthesized materials should be of high interest for applications in nano- and quantum-electronics.

Group IV heteroadamantanes: synthesis of Si6Sn4 and site-selective derivatization of Si6Ge4.

The mixed heteroadamantanes Si6Ge4 and Si6Sn4 are readily accessible from Me2ECl2/Si2Cl6/cat. Cl- (4 × EMe2, 2 × SiCl2, 4 × Si-SiCl3 vertices; E = Ge, Sn). Different from Si6Ge4, two skeletal isomers are formed in the case of Si6Sn4. Site-selective SiCl3-methylation of Si6Ge4 was achieved, leaving the SiCl2 groups untouched.

Dope it with germanium: selective access to functionalized Si5Ge heterocycles.

The Cl- diadduct [nBu4N]2[A·2Cl] of the mixed cyclohexatetrelane (SiCl2)5(GeMe2), A, is accessible from Me2GeCl2, 6 eq. Si2Cl6, and 2 eq. [nBu4N]Cl in one step (96%). Free, tenfold functionalized A can be released from the primary product by decomplexation with AlCl3 (78%). Insight into the assembly mechanism of [nBu4N]2[A·2Cl] and the reactivity of A is provided.

Mixed-Substituted Single-Source Precursors for Si1-xGex Thin Film Deposition.

A series of new mixed-substituted heteronuclear precursors with preformed Si-Ge bonds has been synthesized via a two-step synthesis protocol. The molecular sources combine convenient handling with sufficient thermal lability to provide access to group IV alloys with low carbon content. Differences in the molecule-material conversion by chemical vapor deposition (CVD) techniques are described and traced back to the molecular design. This study illustrates the possibility of tailoring the physical and chemical properties of single-source precursors for their application in the CVD of Si1-xGex coatings. Moreover, partial crystallization of the Si1-xGex has been achieved by Ga metal-supported CVD growth, which demonstrated the potential of the presented precursor class for the synthesis of crystalline group IV alloys.

Selective One-Pot Syntheses of Mixed Silicon-Germanium Heteroadamantane Clusters.

Six Gey alloys are emerging materials for modern semiconductor technology. Well-defined model systems of the bulk structures aid in understanding their intrinsic characteristics. Three such model clusters have now been realized in the form of the Six Gey heteroadamantanes [0], [1], and [2] through selective one-pot syntheses starting from Me2 GeCl2 , Si2 Cl6 , and [nBu4 N]Cl. Compound [0] contains six GeMe2 and four SiSiCl3 vertices, whereas one and two of the GeMe2 groups are replaced by SiCl2 moieties in compounds [1] and [2], respectively. Chloride-ion-mediated rearrangement quantitatively converts [2] into [1] at room temperature and finally into [0] at 60 °C, which is not only remarkable in view of the rigidity of these cage structures but also sheds light on the assembly mechanism.

Trapping Experiments on a Trichlorosilanide Anion: a Key Intermediate of Halogenosilane Chemistry.

Treatment of Si2Cl6 with [Et4N][BCl4] in CH2Cl2 furnished the known products of a chloride-induced disproportionation reaction of the disilane, such as SiCl4, [Si(SiCl3)3]-, and [Si6Cl12·2Cl]2-. No Si-B-bonded products were detectable. In contrast, the addition of Si2Cl6 to [Et4N][BI3Cl] afforded the Si-B adduct [Et4N][I3SiBI3]. Thus, a quantitative Cl/I exchange at the silicon atom accompanies the trihalogenosilanide formation. [Et4N][I3SiBI3] was also accessible from a mixture of Si2I6, [Et4N]I, and BI3. According to X-ray crystallography, the anion [I3SiBI3]- adopts a staggered conformation with an Si-B bond length of 1.977(6) Å. Quantum-chemical calculations revealed a polar covalent Si-B bond with significant contributions from intramolecular I···I dispersion interactions.