Carbon−Carbon Bond Formation in the Surprising Rearrangement of Diorganylzirconium Dialkoxides: Linear Dimerization of Terminal Olefins1

Abstract

The mechanism of the rearrangement of diorganylzirconium dialkoxides, such as R1(R2CH2)Zr(OEt)2, into organylzirconium hydride alkoxides of the type R1R2CHZr(OEt)2H, has been investigated as a function of the R1 and R2 substituents and been found to involve optimally an intramolecular migration of R1 to an sp3-hybridized C−H center. A remarkably rapid transfer hydrozirconation between Bun2Zr(OEt)2 and the olefin RCHCH2 now permits the synthesis of (RCH2CH2)2Zr(OEt)2, whose rearrangement offers a route to the linear olefin dimer R(CH2)4R.