Hafnocene Catalysts for Selective Propylene Oligomerization: Efficient Synthesis of 4-Methyl-1-pentene by β-Methyl Transfer

A series of hafnocene complexes (η5-C5Me4R1)(η5-C5Me4R2)HfCl2 with [R1, R2] = [H, H] (1), [Me,
H] (2), [Me, Me] (3), [Et, Me] (4), [iPr, Me] (5), [SiMe3, Me] (6), [tBu, Me] (7), [nBu, Me] (8), [iBu, Me] (9), [Et,
Et] (10), [nBu, nBu] (11), [iBu, iBu] (12) was tested as catalyst precursors for propylene oligomerization.
Upon activation with methylaluminoxane or [Ph3C][B(C6F5)4]/AliBu3, complexes 2−4 and 8−12 catalyzed
the dimerization of propylene to produce 4-methyl-1-pentene with selectivities ranging from 23.9 to 61.6 wt
% in the product mixture. The selectivity was dependent on the nature of the substituents R1 and R2, with
the highest value found for (η5-C5Me4iBu)2HfCl2 (12). Rapid deactivation was observed for 5−7, whereas
(η5-C5Me4H)2HfCl2 (1) polymerized propylene. 4-Methyl-1-pentene is proposed to form by repeated 1,2-insertion of propylene into the hafnocene methyl cation, followed by selective β-methyl elimination. Detailed
analysis of the byproduct distribution (isobutene, 1-pentene, 2-methyl-1-pentene, 2,4-dimethyl-1-pentene,
4-methyl-1-heptene, 4,6-dimethyl-1-heptene), determined by gas chromatography, was performed with the
aid of a stochastic simulation involving rate constants for the propagation by insertion, β-hydride elimination,
and β-methyl elimination. The rate of termination is dependent on the structure of the growing chain of the
active species as well as on the bulkiness of the cyclopentadienyl ligands. The selectivity highly depends
on the reaction conditions (pressure, temperature, concentration of methylaluminoxane). The rates of
β-methyl elimination leading to 4-methyl-1-pentene were proportional to propylene pressure for 2−4 and
8−10 but practically independent from propylene pressure for the sterically bulkier derivatives 11−12.