Scalable ω-Substituted α-Olefins via Living Chain Transfer Telomerization: A Platform for Next Generation Polyolefins

Isomerically pure, ω-substituted α-olefins of general structure, X-(CH₂)_m(CH₂CH₂)_{n -1}CH = CH₂ (m = 0 or 1; X = alkyl or aryl) (3), have been produced in practical and scalable quantities as narrow Poisson molar mass distributions of separable n-mers (e.g. n = 1 - 10) through a one-pot, two-step process involving: living ternary chain transfer telomerization of tris(ω-substituted alkyl)aluminum, [X-(CH₂)_mCH₂CH₂]₃Al (1), with ethene and a small amount of diethylzinc as a chain transfer mediator, using an in situ generated ion pair initiator derived from the cyclopentadienyl, amidinate (CPAM) Hf pre-initiator, (η⁵-C₅Me₅)[κ²-(N,N')-N(Et)C(Me)N(Et)]HfMe₂ (2) and the borate co-initiator, [PhNHMe₂][B(C₆F₅)₄] (B), followed by catalytic displacement of the trialkylaluminum intermediate using bis(1,5-cyclooctadiene)Ni(0) as the pre-catalyst. Results are further presented for production of several families of "next generation" polyolefins that are obtained through CPAM Zr- and Hf-mediated stereoselective (enantioselective) living coordination polymerization of different derivatives of 3 and including copolymerization with a variety of linear and branched α-olefins and 1,5-hexadiene.