Diacetylenes transition metal complexes

An attractive transformation of cyclic diacetylenes (4) to cyclobutadienes (92) was attempted considering the proximity interaction, but it has been unsuccessful so far. However, transition metal complexes such as the u-cyclopenladienyl cobalt... 

The diyne reactions of 1,4-, 1,5-, 1,6-, and 1,7-diynes via transition metal complexes are useful for the synthesis of new cyclic compounds (Muller, 1974 Wagner and Meier, 1974, 1975). t-C5H5Co(CO)2 reacts catalytically with linear l,m-diacetylenes (XXXVIII) to give trimers (XXXIX), formation of which involves the interaction of six acetylene functions (Vollhardt and Bergman, 1974). 

The outline of this article is as follows. After general remarks tUsout the solid-state polymerization process, adopting the view that it is important to develop new types of solid-state polymerization, the polymerization of the following classes of monomers will be discussed diacetylenes, monoacetylenes, vinyl and diene monomers, cyclic systems which ring open, and transition metal systems. It is implicit in the discussion that appropriately substituted forms of the above monomers may be polymerized as mono-layers and multilayers (11-13) as well as in the form of inclusion complexes (14). Emphasis will be placed on topics of current interest. 

The sterically bulky phosphines (8) have been prepared by the Grignard method from chlorodi(t-butyl)phosphine and chlorodicyclohexylphosphine. In certain iridium(i) complexes, metallation of these phosphines occurs on the terminal olefinic carbon atom. Treatment of a, )-dialkynyl-lithium reagents with chlorodi-(t-butyl)-phosphine gives the diacetylenic diphosphines (9), which form large ring compounds when they form complexes with transition metals. ... 

---