Stannasiloxanes with acyclic, bicyclic, and cubic core structures: X-ray crystal structure of the bicyclic compound [RSi(OSnPh₂O)₃SiR] (R = (2,6-Me₂C₆H₃)NSiMe₃)

Abstract

The reactions of the (arylamino)silanetriols with mono-, di-, and trifunctional alkyl/aryl tin(IV) chlorides have been investigated. Treatment of (arylamino)silanetriols RSi(OH)₃ (1, 2) with Me₃SnCl leads to the isolation of the acyclic stannasiloxanes RSi(OSnMe₃)₃ (R = (2,6-Me₂C₆H₃)NSiMe₃ (3), (2,6-i-Pr₂C₆H₃)NSiMe₃ (4)), which are potential precursors for the preparation of metallasiloxanes. The reactions between the silanetriols 1 and 2 and R'₂SnCl₂ in a 2:3 molar ratio yield the bicylic stannasiloxanes [RSi(OSnR'₂O)₃SiR] (R = (2,6-Me₂C₆H₃)NSiMe₃, R' = Me (5); R = (2,6-Me₂C₆H₃)NSiMe₃, R' = Ph (6); R = (2,6-i-Pr₂C₆H₃)NSiMe₃, R' = Me (7); R = (2,6-i-Pr₂C₆H₃)NSiMe₃, R' = Ph (8)). The cubic stannasiloxanes [RSiO₃SnPh]₄ (R = (2,6-Me₂C₆H₃)NSiMe₃ (9); (2,6-i-Pr₂C₆H₃)NSiMe₃ (10)) are easily prepared in good yields by starting from the respective silanetriols and PhSnCl₃. In all the reactions NEt₃ is used as the hydrogen chloride acceptor. The new stannasiloxanes 3-10 have been extensively characterized by means of their analytical data and mass, IR, and NMR (¹H, ²⁹Si and ¹¹⁹Sn) spectral data. The solid-state structure of the bicyclic compound 6 has been determined by X-ray diffraction studies.