Silicon analogues of the most prominent carbon nanostructures, namely, hollow spheroidals such as C60 and the fullerene family, have been unknown to date. Herein we show that discrete Si20 dodecahedra, stabilized by an endohedral guest and valence saturation, are accessible in preparative yields through a chloride-induced disproportionation reaction of hexachlorodisilane in the presence of tri(n-butyl)amine. X-ray crystallography revealed that each silicon dodecahedron contains an endohedral chloride ion that imparts a net negative charge. Eight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in a strictly regioregular arrangement, a thermodynamically preferred substitution pattern according to quantum-chemical assessment. Our results demonstrate that the wet-chemical self-assembly of a complex, monodisperse Si nanostructure is possible under mild conditions starting from simple Si2 building blocks.
Aiming at the identification of an efficient computational protocol for the accurate NMR assessment of organosilanes in low-polarity organic solvents, (29)Si NMR chemical shifts of a selected set of such species relevant in organic synthesis have been calculated relative to tetramethylsilane (TMS, 1) using selected density functional and perturbation theory methods. Satisfactory results are obtained when using triple zeta quality basis sets such as IGLO-III. Solvent effects impact the calculated results through both, changes in substrate geometry as well as changes in the actual shieldings. Spin-orbit (SO) corrections are required for systems carrying more than one chlorine atom directly bonded to silicon. Best overall results are obtained using gas phase geometries optimized at MPW1K/6-31+G(d) level in combination with shielding calculations performed at MPW1K/IGLO-III level in the presence of the PCM continuum solvation model.
Silicon analogues of the most prominent carbon nanostructures,namely,hollowspheroidals such as C 60 and the fullerene family,have been unknown to date.Herein we show that discrete Si 20 dodecahedra, stabilized by an endohedral guest and valence saturation, are accessible in preparative yields through ac hloride-induced disproportionation reaction of hexachlorodisilane in the presence of tri(n-butyl)amine.Xray crystallography revealed that each silicon dodecahedron contains an endohedral chloride ion that imparts anet negative charge.E ight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in as trictly regioregular arrangement, at hermodynamically preferred substitution pattern according to quantum-chemical assessment. Our results demonstrate that the wet-chemical selfassembly of ac omplex, monodisperse Si nanostructure is possible under mild conditions starting from simple Si 2 building blocks.
The reaction of 4-chloro-1,2-dimethyl-4-supersilylsila-1-cyclopentene (2 a) with Li[NiPr2] at -78 °C results in the formation of the formal 1,4-addition product of the silacyclopentadiene derivative 3,4-dimethyl-1-supersilylsila-1,3-cyclopentadiene (4 a) with 2,3-dimethyl-4-supersilylsila-1,3-cyclopentadiene (5 a). In addition the respective adducts of the Diels-Alder reactions of 4 a+4 a and 4 a+5 a were obtained. Compound 4 a, which displays an s-cis-silacyclopentadiene configuration, reacts with cyclohexene to form the racemate of the [4+2] cycloadduct of 4 a and cyclohexene (9). In the reaction between 4 a and 2,3-dimethylbutadiene, however, 4 a acted as silene as well as silacyclopentadiene to yield the [2+4] and [4+2] cycloadducts 10 and 11, respectively. The constitutions of 9, 10, and 11 were confirmed by NMR spectroscopy and their crystal structures were determined. Reaction of 4-chloro-1,2-dimethyl-4-tert-butyl-4-silacyclopent-1-ene (2 c) with KC8 yielded the corresponding disilane (12), which was characterized by X-ray crystal structure analysis (triclinic, P1). DFT calculations are used to unveil the mechanistic scenario underlying the observed reactivity.
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