Oligomers with silicon, germanium, and transition metal groups: Synthesis and characterization of metal-containing poly[(silylene)diacetylenes] and poly[(germylene)diacetylenes]

Article abstract of DOI:10.1021/om00020a036

In order to prepare polycarbosilanes containing organometallic moieties which could be precursors of transition metal-containing ceramics, poly[(silylene)diacetylenes] (silylene: SiMe₂, SiMePh, SiPh₂) and poly[(methylphenylgermylene)diacetylene] have been reacted with dicobalt octacarbonyl to give the corresponding polymers with approximately halt of the acetylene groups complexed with Co₂(CO)₆ moieties. The introduction of a ferrocenyl group into the main chain of poly[(silylene)diacetylenes] has been achieved by the reaction of the di-Grignard reagent of diacetylene, C₄(MgBr₂), with various 1,1′-bis(chlorodiorganosilyl)ferrocene and led to the synthesis of [-R₂Si-Fc-SiR₂-C≡C-C≡C-]_n (SiR₂: SiMe₂, SiMePh, SiPh₂) (Fc: 1,1′-ferrocene). [-R₂Si-Fc-SiR₂-C≡C-C≡C-SiR′ ₂-C≡C-C≡C-]_n was obtained in the same way by polycondensation of 1,1′-(LiC≡C-C≡C-SiR₂)₂Fc with Cl₂-SiR′₂ (R = Me R′ = Me, Ph; R = R′ = Ph). The reaction of poly[(2,5-diphenyl-1-silacyclopentadiene-1,1-diyl)diacetylene] with Fe₂(CO)₉ and Mo(CO)₄(COD) (COD:cyclooctadiene) gave only the complexation of some of the diene units.