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Electropolymerized films of [Co(v-terpy)2]2+ (v-terpy is 4'-vinyl-2,2':6',2,'-terpyridinyl) exhibit reactivity patterns, especially with regard to ligand exchange, that differ significantly from those exhibited by [Co(terpy)2]2+ in solution. These differences are attributed to the physically constrained environment present in the polymer film. The charge-transport properties follow the model of Dahms and Ruff and the predicted concentration dependence of the diffusion coefficient. These electropolymerized films are also active in the electrocatalytic reduction of carbon dioxide.

Homopolymers and styrene copolymen derived from 4'-viny1-2,2':6',2''-terpyridinyl were prepared in chlorobenzene a t 60 OC by using azobis(isobutyronitri1e) (AIBN) initiation, and monomer reactivity ratios were determined for the styrene copolymers. These polymeric systems containing pendent terpyridinyl ligands readily formed complexes with Co, Cu, and Zn cations. Although vinylterpyridinyl cobalt and ruthenium complex monomers did not undergo homopolymerization with AIBN initiation, they readily formed styrene copolymers under these polymerization conditions. Removal of the metal ions from these polymer-metal complexes occurred readily on washing the complex with acid.ABSTRACT Polymerization of dipropargylsilanes [RR'Si(CH2C4H)2; R, R' = CH3 or Ph] was examined for various transition-metal catalyst systems. A molybdenum complex was found to be a particularly effective catalyst for the cyclopolymerization of dipropargylsilanes. Polymerization of methylphenyldipropargylsilane and diphenyldipropargylsiie by various catalysts leads to soluble, highly colored polymers of average molecular weight 7000-15 000. Polymerization of dimethyldipropargylsilane under the same conditions, however, gives only a partially soluble polymer. IR, 'H NMR, and UV-visible spectroscopies showed that poly(methy1phenyldipropargylsilane) and poly(diphenyldipropargylsi1ane) possess polyene structures having cyclic recurring units in the polymer backbone. Poly(dipropargylsilane)s have been investigated in terms of physical properties, the nature of the doping process, electrical conductivity, and thermal and oxidative stability. The size of substituents was important for the cyclopolymerization tendency and for the resulting polymer properties.

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Electropolymerized films of (Co(v‐terpy)2)2+ (v‐terpy: 4'‐vinyl‐2,2':6',2''‐terpyridinyl) exhibit reactivity patterns, especially with regard to ligand exchange, that differ significantly from those exhibited by (Co(terpy)2)2+ in solution.