Molecular Cage Assembly by Sn−O−Sn Bridging of Di‐, Tri‐ and Tetranuclear Organotin Tectons: Extending the Spacing in Double Ladder Structures

Hydrolysis reactions of di‐ and trinuclear organotin halides yielded large novel cage compounds containing Sn−O−Sn bridges. The molecular structures of two octanuclear tetraorganodistannoxanes showing double‐ladder motifs, viz., [{Me(3)SiCH(2)(Cl)SnCH(2)YCH(2)Sn(OH)CH(2)SiMe(3)}(2)(μ‐O)(2)](2) [1, Y=p‐(Me)(2)SiC(6)H(4)‐C(6)H(4)Si(Me)(2)] and [{Me(3)SiCH(2)(I)SnCH(2)YCH(2)Sn(OH)CH(2)SiMe(3)}(2)(μ‐O)(2)](2) ⋅0.48 I(2) [2⋅0.48 I(2), Y=p‐(Me)(2)SiC(6)H(4)‐C(6)H(4)Si(Me)(2)], and the hexanuclear cage‐compound 1,3,6‐C(6)H(3)(p‐C(6)H(4)Si(Me)(2)CH(2)Sn(R)(2)OSn(R)(2)CH(2)Si(Me)(2)C(6)H(4)‐p)(3)C(6)H(3)‐1,3,6 (3, R=CH(2)SiMe(3)) are reported. Of these, the co‐crystal 2⋅0.48 I(2) exhibits the largest spacing of 16.7 Å reported to date for distannoxane‐based double ladders. DFT calculations for the hexanuclear cage and a related octanuclear congener accompany the experimental work.