Hydrolysis is one of the most common reactions for halides of both tetraand pentacoordinate silicon. In the compounds with an intramolecular coordination, the process might be complicated by the involvement of the coordinating donor atom. We have studied the hydrolysis of pentacoordinate chlorosilanes LCH2Si(R)MeCl (1, R = Me, Ph) with the intramolecular coordination O→Si in mono(C,O)-chelate bidentate monoanionic amidomethyl [LCH2 = R’C(O)NR”CH2; R’ = Alk, Ph; R” = H, Me, CH(Me)Ph], lactamomethyl or imidomethyl (LCH2 or ImCH2, respectively; n = ring size) ligands.

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The title compounds were prepared and X-ray analysis was performed (R = 0.064 and 0.035 for 1309 and 1637 reflections, respectively). In the former the intramolecular S→Si coordination interactions are absent and the Si atom has undistorted tetrahedral coordination with an S...Si distance of 4.034 Å. Crystals of the latter are built of centrosymmetric dimeric H-complexes (S...H(N) 2.58 Å, the S...HN angle 168°).