Synthesis And Properties Of Stannole-containing Polymers By Reaction Of Bis(cyclopentadienyl)titanacyclopentadiene-containing Polymers And Tin(Ⅳ) Chloride

摘要

Polymers having bis(cyclopentadienyl)titana-cyclopentadiene units in the main chain were prepared by the polymerization of a low-valent bis(cyclopentadienyl)-titanium(Ⅱ) complex, generated in situ from bis(cyclopen-tadienyl)titanium dichloride (Cp_2TiCl_2) and n-butyllithium (2 equiv), with internal diynes such as l,4-bis(1-hexynyl)-benzene and 4,4'-bis(1-hexynyl)biphenyl. The bis(cyclopen-tadienyl)titanacyclopentadiene-containing polymers were subjected to the reaction with tin(Ⅳ) chloride, followed by the treatment with methyllithium to give 1,1-dimethylstan-nole-containing organometallic polymers in moderate yields. The stannole containing polymers are soluble in organic solvents, whose number-average molecular weight was estimated to be 2,700-2,800 by GPC. Optical and electrochemical properties of the resulting stannole-con-taining polymers were studied by their UV-vis spectra and cyclic voltammetric analyses, from which they were supposed to have low LUMO energy levels.