Gas-phase reactions of cyclic silanes

Gas Phase Ion-Molecule Chemistry of Carbon, Nitrogen and Oxygen Compounds.

“…In related work, 6 we studied cyclic silanes and showed that silacyclobutanes formed particularly stable pentacoordinate ions, including a unique pentaalkylsilyl anion (C). We also In recent, as yet uncompleted, work we have used silanes to generate the acyl anion (eq.…”

Ion-Molecule reactions in volatile silanes

“…with no evidence of ring cleavage observed. They [84] have also observed several direct additions of allyl anion to substituted silanes. An interesting example is the addition of the allyl anion to l,l-dimethylsi]acyclobutane, viz.…”

“…On the other hand, fluoride ion reacts with l,l-dimethylsilacyclohexane to fom a single ion product, namely, a pentacoordinate silicon adduct, viz. F-+ ~I~I~M e ...... I~M e (111-158) It is most probable that (111-156) and (111-158) are the result of direct fluoride ion adduct fomation and that (111-157) is the result of fluoride ion addi-tion to l,l-dimethylsilacyclobutane followed by cleavage of the strained silacyclobutane ring and loss of ethylene[84].In addition, the product anion of (111-149), namely, (CH3)4SiF -, undergoes fluoride ion transfer with cyclic silanes, viz.…”

Diastereoselective Synthesis of Eight‐Membered‐Ring Allenes from Propargylic Epoxides and Aldehydes by Silylene Insertion into Carbon–Oxygen Bonds

“…[33] Insertions of silylenes into carbon-oxygen bonds do not require release of ring strain from an epoxide. Coordination of the carbonyl group to the Lewis-acidic silicon atom [37] of the strained four-membered-ring silane forms the adduct C in which the aldehyde is activated for carbon-carbon bond formation. (4)].…”