The synthesis and characterization of the metal-poly-yne polymers, poly[trans-bis(tri-nbuty1phosphine)platinum 1,4-butadiynediyl] (I) and poly[trans-bis(tri-n-buty1phosphine)platinum 1,4-phenylenediethynylene] (11), are described. The polymers are synthesized by a condensation reaction between a metal chloride and an acetylene or a metal acetylide complex in amines in the presence of cuprous iodide as a catalyst. Studies of their solution properties suggest that the poly-yne polymers have a rodlike structure and the rodlike condition may result as a feature of trans platinum acetylide moieties. The evidence for the rodlike structure rests on (1) an a value of 1.7 in the Mark-Houwink equation, (2) independence of the intrinsic viscosity from solvent for these polymers, and (3) good agreement of the observed polymer size with that calculated based on an ellipsoid of revolution model.One of the current interests in polymer chemistry lies in multifunctional polymeric materials. In a previous paper' we reported a preliminary result on the synthesis of a new class of polymer having a backbone of conjugated poly-yne and platinum metal atoms. Spectral indicated that poly[trans-bis(tri-n-buty1phosphine)platinum 1,4-butadiynediyl] (I) has all-trans configurations at I1 platinum moieties and polymer I may be expected to have a rodlike structure. The interest in stiff polymers is growing rapidly in terms of their special properties3 in both solution and in the solid state. In this paper we wish to report on the synthesis of poly-yne polymers I and I1 and their solution properties which imply that they have a rigid rodlike structure. Experimental SectionApparatus. Infrared spectra were taken on a Hitachi 295 spectrometer and UV spectra were recorded in methylene chloride with a Shimadzu UV 202 spectrophotometer. 31P NMR spectra were run on a JEOL FXlOO spectrometer. Intrinsic viscosities were measured using Ubbelohde type viscometers at 25 "C. Gel permeation chromatograms were obtained using a Shimadzu-Du Pont Liquid Chromatograph Model 830 and tetrahydrofuran as the mobile phase at room temperature: column set (packed with 0024-9297/78/2211-1063$01.00/0 polystyrene beads made by Shimadzu-Du Pont) HSG 30 (50 cm) + HSG 60 (50 cm); flow rate 1 mL/min; UV 254 nm detector.Monodisperse polystyrenes from Pressure Chemical Co. were used to calibrate the columns. Partial specific volumes ( 8 ) were measured using a semi-self-filling, Ostwald type of picnometer4 in toluene at 25 "C.Preparation of Polymers. Cuprous iodide (7 mg, 0.037 mmol) was added to a deoxygenated solution of trans-bis(tri-n-butylphosphine)bis(l,4-butadiynyl)platinum2 (1.3968 g, 2.0 mmol) and dichlorobis(tri-n-buty1phosphine)platinum (1.3404 g, 2.0 mmol) in 50 mL of diethylamine under a nitrogen atomosphere. The reaction mixture was heated to a gentle reflux with stirring for 1 day and then evaporated to dryness under reduced pressure. In order to remove the cuprous compound, the residue was dissolved in methylene chloride and the resulting solution was filtered by...

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