Polymerization of substituted phenylacetylenes with a novel, water‐soluble Rh–vinyl complex in water

Abstract

Abstract A novel, water‐soluble Rh complex, (nbd)Rh[PPh 2 ( m ‐NaOSO 2 C 6 H 4 )] [C(Ph)CPh 2 ] ( 1 ) was synthesized by the reaction of [(nbd)RhCl] 2 , Ph 2 P( m ‐NaOSO 2 C 6 H 4 ) and Ph 2 CC(Ph)Li, whose structure was determined by NMR and IR spectroscopies. The Rh catalyst 1 induced the polymerization of phenylacetylene (PA) in water to give two kinds of polymers; one was soluble in organic solvents such as tetrahydrofuran (THF) and CHCl 3 , and the other was insoluble in common organic solvents. The polymerization of sodium p ‐ethynylbenzoate ( p ‐NaOCO‐PA) homogeneously proceeded with 1 in water at 60 °C to give the polymer in high yield. Poly( p ‐NaOCO‐PA) was treated with 1 N HCl and then reacted with (CH 3 ) 3 SiCHN 2 to obtain poly( p ‐MeOCO‐PA). The methyl‐esterified polymer was insoluble in THF and CHCl 3 , which suggests that the formed poly( p ‐MeOCO‐PA) has cis–cisoidal structure. The polymer obtained from the polymerization of [ p ‐CH 3 (OCH 2 CH 2 ) 2 O 2 CC 6 H 4 ]CCH with 1 in water was soluble in methanol, ethanol, and THF, and partly soluble in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2100–2105, 2004