Syntheses and Characterization of Bis(silacyclopropene) and Disilabenzvalene

2‐Phospha‐4‐silabicyclo[1.1.0]butane as a Reactive Intermediate

“…[8] Without geometrical constraints, such additions invariably lead to 1,2-diphosphetes of type C by isomerization or direct CÀP insertion. [9] Data on 2,4-disilabicyclo[1.1.0]butanes [10] is limited to two disilabenzvalenes [11] and is absent for the corresponding planar diyls. Only a single 2-silabenzvalene is known, generated by photolysis of a silabenzene.…”

“…[12] For the synthesis of the 2,4-disila derivatives Ando et al applied valence isomerization of bis(silirene) that involves an intramolecular silylene addition to the C = C bond of a silirene. [11] The use of stable silylenes might simplify this approach to a broader array of hetero derivatives, which we decided to explore for the unknown 2-phospha-4-silabicyclo[1.1.0]butanes 4.…”

Facile valence isomerization among bis(silacyclopropenyl), disila(Dewar benzene) and disilabenzvalene

“…Recently, Ando et al [1,2] have reported the crystal structures of bulky group substituted bis(silacyclopropene) (1), disila(Dewar benzene) (3) and disilabenzvalene (4) and inferred that valence isomerization reactions among them are probable (Scheme 1). In their elegant experimental study, they reported that 1 upon mild heating yields 3 and 4 in competitive proportions depending on the nature of substituent on Si and reaction conditions.…”

Palladium and Platinum η2‐Disilyne Complexes Bearing an Isolable Dialkyldisilyne as a Ligand

“…The higher p out orbital in 3 is due to the less-effective p-accepting character of alkyl groups compared to that of trialkylsilyl groups because trialkylsilyl groups adjacent to the p system effectively stabilize the p energy level due to the low-lying s*(Si-C) orbital. [18,19] Although disilyne 3 in the solid state did not decompose in an inert atmosphere at ambient temperature for several months, it isomerizes in solution quantitatively to a diastereomeric mixture of bi(silacyclopropane)s [20] 8 a and 8 b (Scheme 3) in approximately 1:1 ratio within 10 h at ambient temperature. [21,22] Similar C À H insertion was observed in thermal reaction of diaryldisilyne 2.…”