Synthesis and Properties of Stannole-Containing Polymers by Reaction of Bis(cyclopentadienyl)titanacyclopentadiene-Containing Polymers and Tin(IV) Chloride

Abstract

Polymers having bis(cyclopentadienyl)titanacyclopentadiene units in the main chain were prepared by the polymerization of a low-valent bis(cyclopentadienyl)-titanium(II) complex, generated in situ from bis(cyclopentadienyl)titanium dichloride (Cp2TiCl2) and n-butyllithium (2 equiv), with internal diynes such as 1,4-bis(1-hexynyl)-benzene and 4,4′-bis(1-hexynyl)biphenyl. The bis(cyclopentadienyl)titanacyclopentadiene-containing polymers were subjected to the reaction with tin(IV) chloride, followed by the treatment with methyllithium to give 1,1-dimethylstannole-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-containing polymers were studied by their UV-vis spectra and cyclic voltammetric analyses, from which they were supposed to have low LUMO energy levels.