The Diyne Reaction of 1,4-, 1,5-, 1,6-, and 1,7-Diynes via Transition Metal Complexes to New Compounds*

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Abstract
At first an account is given of the discovery of this new diyne reaction and then the formation of new rhodium or iridium complexes is demonstrated by experiments with a series of suitable 1,4-, 1,5-, 1,6-, and 1,7-diyne compounds. All of the transition metal complexes react with practically all alkynes to give new, aromatic systems in controlled syntheses. Also chalcogens react with these complexes. In this manner, a variety of heterocyclic derivatives can be incorporated on to both sides of a quinoidal nucleus to give many new acene quinones. Carbon monoxide, isonitriles, and phenyl azide react analogously with the rhodium complexes. By using suitable diynes, new hetero-substituted seven-membered ring systems can be prepared or, with nickel tetracarbonyl, new cyclooctatetraene derivatives. The rearrangement with palladium complexes leads to substituted azulenes whereas thermal treatment of some rhodium complexes gives rise to linear pentacene quinone derivatives. Polarographic, I. R., and E. S. R. measurements show the validity of the Hammett rule in all cases. As conclusion, a short discussion of a probable mechanism for this diyne reaction is given. 1.New Organo-Transition Metal Complexes 1.1. Reactions between Aromatic Hydrocarbons with o-Diyne Structures and Transition Metals 1.2. Complexes of Aliphatic Systems having a 1,5- or 1,6-Diyne Structure and tris[Triphenylphosphine]rhodium(I) Chloride 1.3. Complexes of Mono- or Diketo-1,5- and -1,6-diyne Systems with tris[Triphenylphosphine]rhodium(I) Chloride 1.4. Complexes of Heterocyclic Systems with Two Alkynic Groups with tris[Triphenylphosphine]rhodium(I) Chloride 2.Reactions of the New Transition Metal Complexes 2.1. Reactions with Alkynes 2.2. Reactions with Chalcogens 2.3. Reactions with Groups Containing "Divalent" Carbon Atoms and with Aryl Azides as Nitrene Precursors 2.4. Preparation of Seven-membered Ring Systems by the Diyne Reaction 2.5. Preparation of Eight-membered Ring Systems by the Diyne Reaction 2.6. Preparation of Substituted Azulenes by the Diyne Reaction 2.7. Other Rearrangements in the Course of the Diyne Reaction 2.8. Attempted Reaction of the Rhodium Complexes with Active "Ene" Components 2.9. Some Physical Measurements on the Quinone Derivatives 3. Mechanisms of the Diyne Reaction and Conclusions

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