Structure-Directing Properties of Lithium Chloride in Supramolecular {4-t-Bu-2,6-[P(O)(OEt)₂]₂C₆H₂}SiH₂Ph·LiCl·2H₂O. Intermolecular PO→Li versus Intramolecular PO→(H)Si Coordination

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).