Polyacetylene Luttinger

One of the most interesting alternatives to the Shirakawa catalyst has been the systems disclosed by Luttinger 22-23) and later elaborated by Lieser et al. 24). The tris(2-cyanoethyl)phosphine complex of nickel chloride reacts with sodium boro-hydride to produce a catalyst system capable of polymerizing acetylene in solutions in either alcohol or, quite remarkably, water. A more efficient catalyst is obtained by replacing the nickel complex with cobalt nitrate. Interest in Luttinger polyacetylene seems to have waned in the last few years. 

The intractability of the early preparations of polyacetylene has severely hampered the establishment of clear-cut relationships between structure, morphology and (electrical) properties. An early example of an integrated approach to structure-property relations is a paper by Haberkom et al. [24], From a combination of x-ray data with NMR and IR investigations, these authors have found a relationship between the content of sp defects and crystallinity in polyacetylene prepared by the Shirakawa, Luttinger and other methods. Such defects are apparently expelled to the amorphous phase. The authors find a correlation with conductivity in both undoped and iodine-doped samples. 

Luttinger. The main advantage of this technique is that the requirement for rigorous exclusion of moisture normally associated with the Ziegler catalyst is circumvented. A new type of polyacetylene film... 

The polymerization of acetylene by using [Rh(l,5-Cod)Cl]2, where 1,5-Cod is c/j,cw-cycloocta-l,5-diene, or [Rh(NBD)Cl]2, where NBD is bicyclo[2,2,I]hepta-2,5-diene, was studied by UV-vis spectroscopy [79,80]. The growing polyacetylene chains were identified by three maxima at 500, 544, and 590 nm as a result of subtracting the spectrum of the catalyst from that of the reaction mixture. The first-order derivative of the absorption spectrum of the growing polyacetylene exhibited vibrational maxima at 480, 515, 550, and 600 nm for the cis-isomer and at 640, 670, and 710 nm for the trans-isomer. UV-vis and FTIR spectroscopies were used in the study of the structure of thin freestanding films of cis- and trans-PA obtained by using Rh(I) complexes. The absorption spectrum shows no vibrational structure, which was detected in acetylene polymerization in ethanol. The microstructure of PA is very similar to that of PA synthesized with a Luttinger catalyst in terms of sp defects in the polymer chains detected by FTIR spectroscopy. 

Terlemezyan, L. Mihailov, M. On the configuration of polyacetylene obtained by Luttinger s catalyst Makromol. Chem., Rapid Commun. 1982,3, 613-161. 

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