The reaction of SnBr 4 with in situ generated 2,4,6-trimethylphenylmagnesium bromide afforded a mixture of (2,4,6-Me 3 C 6 H 2 ) 2 SnBr 2 (1) and (2,4,6-Me 3 C 6 H 2 ) 3 SnBr (2) which could be separated from each other by their solubility differences in diethyl ether. On the other hand, the reaction of tin metal with 2,4,6-Me 3 C 6 H 2 CH 2 Br afforded (2,4,6-Me 3 C 6 H 2 CH 2 ) 2 SnBr 2 (3). Hydrolysis of the latter using triethylamine as the base afforded [{(2,4,6-Me 3 C 6 H 2 CH 2 ) 2 Sn} 2 (μ-O)(Br)(μ-OH)] 2 ⋅2CH 2 Cl 2 (4) while the use of NaOH as the base afforded [{(2,4,6-Me 3 C 6 H 2 CH 2 ) 2 Sn} 2 (μ-O)(OH)(μ-OH)] 2 ⋅2CH 2 Cl 2 (5). Compounds 4 and 5 are dimeric tetraorganodistannoxanes consisting of a central distannoxane (Sn 2 O 2 ) motif.