SYNTHESIS, REACTIONS AND CATALYTIC ACTIVITIES OF WATER-SOLUBLE RHODIUM AND IRIDIUM-SULFONATED TRIPHENYLPHOSPHINE COMPLEXES - 1 - POLYMERIZATION OF TERMINAL ALKYNES

Polymerization of terminal alkynes (phenylacetylene and 4-ethynyltolue ne) catalyzed by water soluble rhodium (I) complex, RhCl(CO)(TPPTS)(2) (TPPTS=m-P(C6H4SO3Na)(3)) (1) selectively produces cis-transoid polym ers at room temperature in homogeneous solution of H2O and MeOH as wel l as in biphasic solutions of H2O and CHCl3. The rate of polymerizatio n is higher in H2O/MeOH than in H2O/CHCl3. The iridium analog, IrCl(CO ) (TPPTS), (2) shows catalytic activity for the polymerization of phen ylacetylene only at elevated temperature to give trans-polymers. The p olymerization rate increases significantly when the trimethylamine N-o xide (Me3NO) was added to the reaction mixtures. The electronic absorp tion spectra of the cis-transoid polymers show three absorption bands whereas the trans-polymers show only one absorption band. It seems tha t the electronic absorption bands depend on the configuration of the p olymers.