Restricted Rotation about the P−C Bond in the Triorganosilane {4-t-Bu-2,6-[P(O)(O-i-Pr)₂]₂C₆H₂}SiPh₂H:  Identification of a Novel Rotamer and Its Conversion to the Siliconium Salt {4-t-Bu-2,6-[P(O)(O-i-Pr)₂]₂C₆H₂}SiPh₂⁺PF₆^-

Abstract

The syntheses and structures of the [4 + 1]-coordinated triorganosilane {4-t-Bu-2,6-[P(O)(O-i-Pr)2]2-C6H2}SiPh2H (5) and of the intramolecularly coordinated triorganosiliconium hexafluorophosphate {4-t-Bu-2,6-[P(O)(O-i-Pr)2]2C6H2}SiPh2 +PF6 - (6) are reported. In the solid state, compound 5 adopts a rotameric form that differs from those found for {4-t-Bu-2,6-[P(O)(OEt)2]2-C6H2}SiPh2R (R = Ph, H).

Anionic 1,4-Silyl Migration in (2-(Trimethylsilyl)phenyl)phosphonium Methylides

“…The intramolecular 1,5-type interaction between an electron-donating heteroatom (Y) and a tetracoordinate silicon, which are linked to each other through the o -phenylene skeleton (Figure ), has been widely studied, because this type of interaction sometimes realizes the hypercoordination at the silicon . A number of coordinating groups (−X−Y) are available, such as −CH 2 −Y (Y = NR 2 , OR, PR 2 , SR), , −CF 2 −F, −NR‘−NR 2 , −NNR, and −P(OR) 2 O 1 Representative coordinating groups in 1,5-type interactions in hypercoordinate silicon compounds. …”

The UV‐Light Initiated Reaction of Organosilanes with Tungsten Hexacarbonyl: Formation of an Organosilylene Complex and Organosilylium Salts

“…The silicon atom in 2 adopts a distorted trigonal-bipyramidal configuration (geometrical goodness [43][44][45] ∆Σ(θ) = 56.5°) with C(1), C (21) [33] whereas the long distance is similar to the P=O→Si distance determined for the benzoxasilaphosphole [1(P),3(Si)-…”

“…For some years we have been interested in the application of phosphorus-containing O,C,O-coordinating pincer-type ligands to the synthesis of, among others [33][34][35][36], intramolecularly coordinated organoelement compounds of types (A) -(E) (Figure 1) [37,38].…”

The Role of Monoanionic Aryl Pincer Ligands in the Stabilization of Group 14 Metallylenes

“…Even though there are several examples of tetravalent silicon species with pincer type ligands, [14][15][16] up to date there are no examples of divalent silicon derivatives stabilized by these ligands. The first examples for N,C,N-pincer ligand stabilized divalent germanium derivatives were presented by Bibal et al, with diethylaminomethyl groups as ortho substituents (L I ), obtained through the reaction of 2,6-bis(dialkylaminomethyl)-phenyl bromide (alkyl = Et, i-Pr) with n-BuLi then reaction with GeCl2•dioxane, as shown in Scheme 3.…”