“…In Hengge's group much attention was focused on cyclosilane chemistry . Some relatively recent work had utilized Vyazankin chemistry 2 to obtain (undecamethylcyclohexasilanyl)potassium ( 2 ) from the respective bis(undecamethylcyclohexasilanyl)mercury compound ( 1 ) (eq 1). , Such potassium derivatives proved to be very useful for the synthesis of higher polysilanes. …”
The author's rather accidental discovery of the synthesis of [tris(trimethylsilyl)silyl]potassium by reaction of tetrakis(trimethylsilyl)silane with potassium tert-butoxide in 1996 was the starting point for the continuation of some chemistry reported by earlier workers which had been mostly dormant for almost 30 years. The reaction of polysilanes with potassium alkoxides was found to be superior to analogous chemistry using methyllithium. The high selectivity for the cleavage of peripheral trimethylsilyl groups allowed not only the preparation of higher polysilanyl anions but also of dianions. The latter are especially useful for the synthesis of cyclic and also bicyclic polysilanes, including heterocyclic compounds. The incorporation of heteroatoms into the starting materials gave silyl anions with ambiphilic character. (Polysilanyl)potassium compounds were used to prepare a number of transition-metal compounds, including the first example of an early-transition-metal disilene complex. Recent studies have shown that the method of anion formation via the reaction of silylated precursors with potassium tert-butoxide works equally well with carbon, germanium, and tin compounds.
“…In Hengge's group much attention was focused on cyclosilane chemistry . Some relatively recent work had utilized Vyazankin chemistry 2 to obtain (undecamethylcyclohexasilanyl)potassium ( 2 ) from the respective bis(undecamethylcyclohexasilanyl)mercury compound ( 1 ) (eq 1). , Such potassium derivatives proved to be very useful for the synthesis of higher polysilanes. …”
The author's rather accidental discovery of the synthesis of [tris(trimethylsilyl)silyl]potassium by reaction of tetrakis(trimethylsilyl)silane with potassium tert-butoxide in 1996 was the starting point for the continuation of some chemistry reported by earlier workers which had been mostly dormant for almost 30 years. The reaction of polysilanes with potassium alkoxides was found to be superior to analogous chemistry using methyllithium. The high selectivity for the cleavage of peripheral trimethylsilyl groups allowed not only the preparation of higher polysilanyl anions but also of dianions. The latter are especially useful for the synthesis of cyclic and also bicyclic polysilanes, including heterocyclic compounds. The incorporation of heteroatoms into the starting materials gave silyl anions with ambiphilic character. (Polysilanyl)potassium compounds were used to prepare a number of transition-metal compounds, including the first example of an early-transition-metal disilene complex. Recent studies have shown that the method of anion formation via the reaction of silylated precursors with potassium tert-butoxide works equally well with carbon, germanium, and tin compounds.
“…In con tinuation of these studies and our research on the synthe sis 11-13 of dichloro derivatives of permethyloligosilanes, which serve as synthons in the synthesis of polymers con taining oligosilane fragments in the main chain by differ ent macromolecular design, we examined the reaction of SbCl 5 with yet another representative of permethyl oligosilanes, viz., branched tetrakis(trimethylsilyl)silane (Me 3 Si) 4 Si (1), and investigated the characteristic fea tures of fragmentation of bifunctional derivatives of si lane 1 under electron impact ionization (EI). In con tinuation of these studies and our research on the synthe sis 11-13 of dichloro derivatives of permethyloligosilanes, which serve as synthons in the synthesis of polymers con taining oligosilane fragments in the main chain by differ ent macromolecular design, we examined the reaction of SbCl 5 with yet another representative of permethyl oligosilanes, viz., branched tetrakis(trimethylsilyl)silane (Me 3 Si) 4 Si (1), and investigated the characteristic fea tures of fragmentation of bifunctional derivatives of si lane 1 under electron impact ionization (EI).…”
Bifunctional derivatives (XMe 2 Si) 2 Si(SiMe 3 ) 2 (X = H, Cl, or OH) were synthesized for the first time by the reaction of tetrakis(trimethylsilyl)silane with SbCl 5 . The molecular and crystal structure of bis(hydroxydimethylsilyl)bis(trimethylsilyl)silane was established by X ray diffrac tion. The fragmentation of the resulting compounds under electron impact was studied by mass spectrometry.Key words: tetrakis(trimethylsilyl)silane, antimony pentachloride, bifunctional tetra kis(trimethylsilyl)silane derivatives, X ray diffraction study, mass spectrometry.* The reaction products were identified based on empirical mass spectrum-structure relationships.
Introduction
General Methods for Cyclopolysilane Synthesis
General Properties of Cyclopolysilanes
Monocyclic Silanes
Polycyclic Silanes and Cages
Transition Metal Containing Cyclopolysilanes
Acknowledgments
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