Reaction of disilagermirenes with phenylacetylene: from a germasilene GeSi to a metalladiene of the type SiGeCC

The reaction of tetrakis[di-tert-butyl(methyl)silyl]-2-disilagermirene (1b) with phenylacetylene at room temperature produced highly air- and moisture-sensitive bright orange crystals of 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene (2b), which represents a previously unknown metalladiene with one SiGe and one CC double bond. The crystal structure of 2b was determined by X-ray crystallography, which showed a trans-bent configuration around the SiGe double bond with a bond length of 2.250(1) Å. The reaction mechanism to form 2b, the question of conjugation of the two double bonds in a cyclopentadiene ring of 2b, as well as its reactivity are discussed. The reaction of tetrakis[di-tert-butyl(methyl)silyl]-1-disilagermirene (1a), which is an isomer of 1b, with phenylacetylene is also examined.