Synthesis and properties of polysilane-poly(ferrocenylsilane) random copolymers and oxidized poly(ferrocenylsilane)s

grantor: University of TorontoPoly(ferrocenylsilane)s are polymers which feature alternating ferrocene and organosilane units. The synthesis of polymers that may have interesting electrical properties and which feature the ferrocenylsilane unit is herein outlined. Polysilane-poly(ferrocenylsilane) copolymers are synthesized by the thermal ring-opening co-polymerization of a (1) silaferrocenophane and a cyclotetrasilane. These polymers were found to be random in nature, containing short silane and ferrocenylsilane segments. Oxidized poly(ferrocenylsilane)s are synthesized by the reaction of poly(ferrocenylsilane)s with a number of one-electron oxidants. Molecular weight decline occurred throughout the course of the oxidation (and, in the case of one counterion, in the solid state afterward), but this decline could be minimized by the addition of methyl groups to the cyclopentadienyl rings of the ferrocenyl units, and the use of a mild one-electron oxidant $(\lbrack (p$-$\rm BrC\sb6H\sb4)\sb3N\rbrack \lbrack PF\sb6\rbrack ).$ Also, the crystal structure of an oxidized oligomer was determined.M.Sc