Synthesis and characterization of novel heteroannular benzoylferrocene polysiloxane monomers, oligomers, and polymers

Copoly[2,2'-bis[1,1'-ferrocene]benzoylylene/3,3,5,5-tetramethyl-4-oxa-3,5-d isila-1,7-heptanylene] (III) was synthesized by two approaches. High molecu lar weight III was obtained by an acid catalyzed equilibrium condensation o f 1,1'-bis[1-(3',3',5',5'-tetramethyl-4-oxa-3,5-disilahexyl)benzoyl] ferroc ene (IV), while lower molecular weight III was synthesized by the dihydrido carbonyltris(triphenylphosphine)ruthenium (Ru) catalyzed co-oligomerization of 1,1'-benzoylferrocene and 1,3-divinyltetramethyl-disiloxane. Ru catalyz ed reaction of benzoylferrocene and 1,3-divinyltetramethyl-disiloxane gave 1-[2'-ferrocenoylphenethyl]-3-vinyltetramethyl-disiloxane (II), 1,3-bis[2'- ferrocenoyl phenethyl]tetramethyldisiloxane (I). The electrochemistry of I, III, and IV have been examined by cyclic voltammetry. These materials show a single reversible oxidation process. The products have been characterize d by H-1, C-13, Si-29 NMR, IR, UV-Vis spectroscopy, as well as elemental an alysis and/or high resolution mass spectrometry with peak matching. GPC, DS C and TGA of the copolymer and co-oligomer III have been determined. (C) 19 99 Elsevier Science Ltd. All rights reserved.