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An organosilicon cage compound containing the sila-adamantane structural unit, which is the building block of crystalline silicon, was synthesized by the Lewis acid-catalyzed rearrangement reaction of a structural isomer.
Cyclohexane, with its well-defined conformers, could be an ideal force-controlled molecular switch if it were to display substantial differences in electronic and optical properties between its conformers. We utilize σ conjugation in heavier analogues of cyclohexanes (i.e. cyclohexasilanes) and show that 1,4-disubstituted cyclohexasilanes display… (More)
Over the last few years our group has been strongly involved in the study of the chemistry of oligosilanes. 1,2 In particular, the development of a convenient synthetic access to structurally diverse oligosilanyl anions 3À6 allowed the preparation of a huge variety of previously unknown small polysilanes. Some 40 years ago Ishikawa and Kumada discovered the… (More)
Lewis acid-catalyzed rearrangement reactions of trimethylgermylated small permethylated oligosilanes were found to show a strong tendency of the germanium atoms to move to the more highly silylated positions of the molecule. This makes possible the construction of molecules with high germanium content in the core parts of the molecules by the following… (More)
Possessing the property of sigma-bond electron delocalisation, polysilanes are a class of compounds with unique properties. In recent years major progress has been achieved in the theoretical understanding and the synthesis of polysilanes. Much insight into the connection between conformation and electronic properties has been gained from studies of defined… (More)
Reaction of the PEt 3 adduct of a disilylated five-membered cyclic germylene with group 4 metallocene dichlorides in the presence of magnesium led to the formation of the respective germylene metallocene phosphine complexes of titanium, zirconium, and hafnium. Attempts to react the related NHC adduct of a disilylated four-membered cyclic germylene under the… (More)
b S Supporting Information ' INTRODUCTION In recent years small alkylated polysilanes 1 have been used to investigate the conformational dependency of the σ-bond electron delocalization of these compounds. 2À8 Some reports have dealt with branched derivatives of this substance class, which were either den-drimers 9À14 or linear silanes with branched end… (More)
Reaction of the magnesium transmetalation product of a 1,2-dipotassiodisilane with hafnocene dichloride gives a disilene hafnocene complex. X-ray crystallography of the respective trimethylphosphane adduct provides structural proof for this assignment.