Silyl ketenes provide an interesting
class of molecules to be used
as building blocks for highly functional molecules and materials,
including as monomers in chain growth polymerizations, whereas previous
work suggests that both the carbon–carbon and carbon–oxygen
double bond of silyl ketenes can undergo polymerization; no selectivity
was observed and secondary reactions occurred. Herein, we report the
oligomerization of tert-butyldiphenyl silyl ketene,
in which polymerization of the carbon–carbon double bond is
accompanied by a Brook rearrangement to give a polysilyl enol ether
structure. Computational studies support that this oligomer has a
rigid rod structure and is highly polarizable, which is of potential
value as a dielectric material. Experimentally, the impact of initiator,
solvent, and reaction time is evaluated, and product identity is verified
by 2D nuclear magnetic resonance studies. In the presence of a solvent
and extended reaction times, intrachain backbiting occurs to yield
two cyclic small molecules that were isolated and fully characterized,
and mechanisms are proposed for their formation. At shorter reaction
time or under solvent-free conditions, linear oligomers were isolated,
and use of a bifunctional initiator led to the production of oligomers
with molecular weight consistent with that expected based on the monomer-to-initiator
ratio and percent monomer consumption. This work illustrates that
silyl ketenes are intriguing and exciting building blocks for polymers,
and ongoing work addresses the characterization of the physical properties
of the materials and identifying conditions for the controlled polymerization
of the carbon–oxygen double bond.