On the structures of pentasilicon dodecachloride, Si5Cl12, and hexasilicon tetradecachloride, Si6Cl14

Systematic synthesis in the polysilane series

“…Nuss determined that complexes could be formed with other chlorosilanes such as methyltrichlorosilane and dimethy ldichlorosilane, but not with trimethylchlorosilane. 22 On the hypothesis that these complexes were donor complexes, utilizing the nonbonding pairs of the monosilane chlorines, the failure of trimethyltrichlorosilane to form a complex with either of these perchloropolysilanes suggests structural inhibition. In a careful study of the dissociation energies of these complexes it was determined that symmetry of the donor chlorosilane also was important.…”

Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study

“…Employing catalytic amounts of amine and varying reaction conditions, Urry and co‐workers as well as Wiberg and Neumaier reported quantitative formation of well‐defined products of the conjectured compositions Si 5 Cl 12 or Si 6 Cl 14 . Ambiguities with respect to the constitution of the reaction products were resolved by X‐ray diffraction analysis disclosing neo ‐Si 5 Cl 12 ⋅ SiCl 4 as the only reaction product without further evidence for Si 6 Cl 14 . Subsequently, the diverse reactivity of hexachlorodisilane ( 1 ) with Lewis bases such as amines, phosphines and phosphine oxides, N‐heterocyclic carbenes, as well as chloride‐ions has been subject to detailed studies, most of which assign a key role to a (base‐stabilized) dichlorosilylene intermediate.…”

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

“…The underlying mechanistic pathways are characterized by the tendency of covalent Si–Si bonds to undergo rearrangement reactions, a dynamic behavior that can be triggered deliberately by the addition of Lewis bases. As one of the first examples, Urry and co-workers reported that hexachlorodisilane (Si 2 Cl 6 ) undergoes quantitative transformation to perchlorinated neopentasilane Si­(SiCl 3 ) 4 and SiCl 4 upon the catalytic action of various trialkylamines (R 3 N). − …”