Silicon-chalcogen rings

Addition of elemental chalcogens to the double bonds between silicon and phosphorus gives three-membered ring compounds (Scheme 9).59 A 1,2-di-bromodigermene reacts with S8 to give the four-membered ring compound,60 in... 

Se 374, the products are four-membered rings, as illustrated for 61 in equation 108. These products may arise from dimerization of a silicon-chalcogen doubly bonded intermediate. 

In view of the preference of the tetrasilabuta-1,3-diene 139 for the s-cis form, it seemed worthwhile to examine its behavior in [4 + 2] cycloadditions of the Diels-Alder type. Since 139, like many disilenes, should behave as an electron-rich diene, we attempted to react it with various electron-poor and also with some electron-rich olefins. No reaction was detected in any case. Only in the presence of water did 139 react with quinones to furnish the unsymmetrically substituted disilenes 36 and 37 (see Section III.A). The effective shielding of the double bonds by the bulky aryl groups and, above all, the 1, 4-separation of the terminal silicon atoms of about 5.40 A appear to be responsible for these failures. Thus, it was surprising that treatment of 139 with the heavier chalcogens afforded five-membered ring compounds in a formal [4 + 1] cycloaddition (see below). 

Since genuine [4-1-2] cycloaddition products had previously not been prepared, it was surprising to find that the action of sulfur on 24 resulted in a formal [4-I-1] cycloaddition to furnish the first ftve-membered ring with an endocyclic silicon-silicon double bond 25. The heavier chalcogens selenium and tellurium did not react with 24. However, in the presence of small amounts of triethylphosphane smooth reactions with these elements did occur to furnish two further ftve-membered ring compounds 26, 27, each with an endocyclic silicon-silicon double bond (Eq. 8) [14]. 

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