Synthesis and reactions of polythiadisilabicyclo [k.l.m] alkanes having Unusual Bond-Order

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The reaction of tris (trimethylsilyl) methylsilane (TsiSiH_3) with elemental sulfur afforded 1,3-bis {tris (trimethylsilyl) methyl}-2,4,5,6,7,8-hexathia-1,3-disilabicyclo [3.2.1] octane (6), 1,3-bis {tris (trimethylsilyl) methyl}-2,4,5,6,7-pentathia-1,3-disilabicyclo [2.1.1] heptane (b5), and 1,3-bis {tris (trimethysilyl) methyl}-2,4,5,6-tetrathia-1,3-disilabicyclo [2.1.1] hexane (4)in 12%, 12%, and 22% yields respectively. Structures of these compounds were confirmed by X-ray diffraction analysis. 1,3-Bis {tris (trimethylsilyl) methyl}-2,4,5-trithia [1.1.1] pentane (3) was obtained by photolysis of 4 in the presence of trimethylphosphine, quantitatively. The distance between the bridgehead silicon atoms of 2.407 A in 3 lies in the range of common Si-Si single bonds.