Silanediols Derived from Silanetriols. X‐ray Crystal Structures of (2,4,6‐Me 3 C 6 H 2 )N(SiMe 3 )Si(OSiMe 3 )(OH) 2 and (2,4,6‐Me 3 C 6 H 2 )N(SiMe 3 )Si(OSiMe 2 R)(OH) 2 [R = CH 2 (2‐NH 2 ‐3,5‐Me 2 C 6 H 2 )]

The silanediols RN(SiMe 3 )Si(OSiMe 3 )(OH) 2 (R = 2,4,6‐Me 3 C 6 H 2 4 , 2,6‐Me 2 C 6 H 3 5 , and 2,6‐ i Pr 2 C 6 H 3 6 ) were prepared by the reactions of the respective silanetriols RN(SiMe 3 )‐Si(OH) 3 1 – 3 with SiMe 3 Cl in THF/hexane. Silanetriol 1 in CH 2 Cl 2 /hexane solution converts over a period of 4 weeks into the silanediol (2,4,6‐Me 3 C 6 H 2 )N(SiMe 3 )Si(OSiMe 2 R)‐(OH) 2 [R = CH 2 (2‐NH 2 ‐3,5‐Me 2 C 6 H 2 )] ( 7 ). Compounds 4 – 7 were characterized by means of mass, IR and NMR ( 1 H and 29 Si) spectroscopy. Additionally, the molecular structures of 4 and 7 were determined by single‐crystal X‐ray diffraction studies. Compound 4 forms O H…O hydrogen‐bonded tetramers in the solid state. A nine‐membered ring formed by an intermolecular OH…N hydrogen bond is found in the solid‐state structure of 7 .