The synthesis of the novel diorganosilanes {4-t-Bu-2,6-[P(O)(OR)2]2C6H2}Si(H)2Ph (5, R = Et; 6, R
= i-Pr) is reported. Compound 5 reacts with lithium chloride in the presence of air moisture to give the
complex 5·LiCl·2H2O (5a). The crystal and molecular structures of the diorganosilane 6 and complex
5a were determined by single-crystal X-ray diffraction analysis. The latter compound shows unprecedented
(5·Li+)6 hexamers which are further linked by water to give a two-dimensional coordination polymer.
The reaction of compound 6 with [Ph3C]+PF6
- provided in situ a mixture of the triorganosiliconium
salts {4-t-Bu-2,6-[P(O)(O-i-Pr)2]2C6H2}Si(X)Ph+PF6
- (7, X = H; 8, X = F), whereas reaction with CCl4
gave a mixture of the benzoxasilaphospholes [1(P),3(Si)-P(O)(O-i-Pr)OSi(X)Ph-6-t-Bu-4-P(O)(O-i-Pr)2]C6H2 (9, X = H; 10, X = Cl).
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).
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