GAS-PHASE OF METHYL(TRIMETHYLSILYL)GERMYLENE

The products obtained from the vacuum flow pyrolysis of (Me3Si)(2)GeHM e in the presence of excess 2,3-dimethylbutadiene point to the generat ion of the alpha-silylgermylene Me3Si-Ge-Me, and to its rearrangement via intramolecular C-H insertion to form a silagermirane whose ring-op ening lends to isomeric beta-silylgermylenes. Dimerization of Me3Si-Ge -Me to a digermene followed by a sequence of rearrangements is also in dicated. Fragmentation of silagermirane intermediates to a heteroene a nd a divalent species is an important process under these conditions. No products were found that demand the rearrangement of Me3Si-Ge-Me to Me2Si=GeMe2 via a methyl shift. (C) 1997 Elsevier Science Ltd.