Oxidative Polymerization of Silylthioketene Dimer

Abstract

Summary: The first π‐conjugated poly(thioketene dimer) was synthesized via the homopolymerization of a silylthioketene dimer by a chemical oxidation‐reduction process. The polymerization of trimethylsilylthioketene dimer in the presence of FeCl3 (in CHCl3 at 70 °C for 24 h) gave the corresponding doped poly(thioketene dimer). After treatment of the doped polymer with an aqueous solution of ammonia, the neutral poly(thioketene dimer) was obtained with an incidental desilylation. The polymer obtained was soluble in DMF and DMSO. From gel permeation chromatographic analysis (DMF, polystyrene standards), the number‐average molecular weight of the polymer was found to be 7 460. The polymer showed low oxidation potentials derived from the thioketene dimer unit. An effective extension of the π‐conjugation was observed in the polymer.Synthesis of π‐conjugated poly(thioketene dimer).magnified imageSynthesis of π‐conjugated poly(thioketene dimer).

Functional polymers based on electron-donating TTF and derivatives

“…A dimeric product of the [2+2] cycloaddition of trimethylsilylthioketene, 2,4-bis(trimethylsilylidene)-1,3-dithietane 56b can be used directly for polymerization via oxidative polymerization (Scheme 16). 108 The chemical oxidative polymerization of 56b with FeCl 3 in CHCl 3 proceeded along a similar reaction scheme with the dimerization reaction of dithiafulvenes to give a cationic polymeric product. Then the reduction of the polymer by an NH 3 solution gave a neutral polymer 59 together with the elimination of the trimethylsilyl group, this was confirmed by NMR, IR, elemental analysis.…”

Synthesis and thermal stability of imino-1,3-dithietanes. Influence of structural factors

“…5 Imino 1,3 dithietanes are structural units of polymers that form complexes with tetracyanoquino dimethane having high conductivity. 6 1,3 Dithietanes are poorly known because these com pounds are difficult to synthesize. 2 More or less general methods for the synthesis of these compounds are few in number: the dimerization of head to tail thiocarbonyl compounds promoted by heating, 7 photochemical action, 8 bases, 9 acids, 10 or other methods and the dimerization of thioketones.…”

“…Hence, we per formed the reactions of isonitriles 2a-e with a series of 1,2 dithiol 3 thiones, both monocyclic derivatives containing two substituents (4,5) or one substituent (6,7) in the ring, and fused derivatives containing hetero cyclic (8)(9)(10), cyclohexane (11), or benzene (12) rings.…”