Journal of Organometallic Chemistry p. 353 - 366 (1980)
Update date:2022-08-16
Topics:
Datta, S.
Fischer, M. B.
Wreford, S. S.
The complex Ti(η-C4H6)2 (dmpe) (dmpe = 1,2-bis(dimethylphosphino)ethane) was prepared by Na/Hg reduction of TiCl4 (dmpe) in the presence of butadiene.The compound is a poorer Lewis base than is Zr(η-C4H6)2(dmpe), as it fails to form seven-coordinate adducts analogously to the Zr complex.Both complexes catalyze the dimerization of ethylene to 1-butene and, by cross dimerization with additional ethylene, 3-methyl-1-pentene and 2-ethyl-1-butene.Propene is converted to 2,3-dimethyl-1-butene. cis-2-Butene is very slowly dimerized to 3,4-dimethyl-1-hexene.On the basis of the products formed and their distribution, a mechanism involving formation of a metallocyclopentane complex is proposed.The reaction is first-order in olefin and is slowed by increasing substitution.Formation of a mono(olefin) complex is the probable rate-determining step.
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