Cyclooctadiene complexes with copper

Poly(l,4-butadiene) segments prepared by the ruthenium-mediated ROMP of 1,5-cyclooctadiene can be incorporated into the ABA-type block copolymers with styrene (B-106) and MMA (B-107).397 The synthetic method is based on the copper-catalyzed radical polymerizations of styrene and MMA from the telechelic poly(butadiene) obtained by a bifunctional chain-transfer agent such as bis(allyl chloride) or bis-(2-bromopropionate) during the ROMP process. A more direct route to similar block copolymers is based on the use of a ruthenium carbene complex with a C—Br bond such as Ru-13 as described above.67 The complex induced simultaneous or tandem block copolymerizations of MMA and 1,5-cyclooctadiene to give B-108, which can be hydrogenated into B-109, in one pot, catalyzed by the ruthenium residue from Ru-13. 

Dien-4-ynes 136 (R -R = alkyl) are produced from propargylic carbonates 135 and terminal alkynes in the presence of a palladium-phosphine complex and copper(I) iodide. The linear co-dimerization of terminal acetylenes and 1,3-dienes is catalyzed by ruthenium(cyclooctadiene)(cyclooctatriene)(trialkylphosphine) (alkyl = Et, Bu or octyl) thus 1-hexyne and methyl penta-2,4-dienoate give a mixture of the eneynes 137 and 138. Coupling of octa-l,7-diyne (139) with the acetylenic bromo acid 140 in aqueous THF-methanol containing butylamine, hydroxylamine hydrochloride and copper(I) chloride gave a mixture of the triynyl acids 141 and 142. ... 

Electrolysis at copper electrodes of cupric perchlorate with 1,5-cyclooctadiene in methanol yields well-defined crystals of an air-stable cuprous complex (CgHi2)2CuC104 (390). The C=C stretching band at 1660 cm in the diene is replaced by two bands at 1638 and 1595 cm" in the complex, suggesting nonequivalent coordination of the double bonds. As with the silver-olefin complexes (492) there is a dependence... 

For olefin Ti-complexes, copper(II) halides as fine powders react with butadiene, norbornadiene, cyclooctadiene or dicyclopentadiene to give the corresponding olefin complex (2-4). Some olefins readily form silver nitrate complexes (2-5) in an aqueous or alcoholic solution. 

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