Synthesis, X-ray Structural Analysis, and Ethylene Polymerization Studies of Group IV Metal Heterobimetallic Aluminum-Pyrrolyl Complexes

The synthesis, structural characterization, and ethylene polymerization performance of heterobimetallic aluminum-pyrrolyl complexes of group IV metals are described. The combination of MCl4 (M = Ti, Zr, Hf), aluminum alkyls and pyrroles leads, depending on stoichiometry, to mono- and bis(aluminum-pyrrolyl) complexes that are remiscent of the corresponding mono- and bis- cyclopentadienyl systems. The bis(aluminum-pyrrolyl) complexes (eta(5)-2,5-Me2C4H2NAlClMe2)(2)TiMe2 (1), zirconium (eta(5)-2,5-Me2C4H2NAlClMe2)(2)ZrClMe (2), (eta(5)-2,5-Me2C4H2NAlCl2Et)(2)ZrCl2 (3), and hafnium (eta(5)-2,5-Me2C4H2NAlClMe2)(2)HfClMe (4) were found to be inactive toward ethylene polymerization. By contrast, the electron-deficient mono(aluminum-pyrrolyl) piano stool complexes (eta(5)-2,5-Me2C4H2NAlCl2Me)TiCl2Me (5), (eta(5)-2,3-Me2C8H4NAlCl2Me)TiCl2Me (6), and (eta(5)-3,4,5,6-Ci(2)H(12)NAlCl(2)Me)TiClMe2 (7), obtained by treatment of TiCl4 with equimolar amounts of trimethyl aluminum and the corresponding pyrrole ligands, were found to be moderately active for ethylene polymerization with MAO or [Ph3C+][B(C6F5)(4)](-), in all cases producing UHMWPE. The NMR scale reaction of 5 with B(C6F5)(3) showed the formation of a solvent-separated ion pair, formed by the abstraction by B(C6F5)(3) of a methyl group from Al-CH3 rather than from Ti-CH3. H-1 and C-13 NMR analysis of 6 and 7 revealed that several stable structural isomers exist in solution, with a slow interconversion on the NMR time scale. The dimeric zirconium complexes [(eta(5),kappa(1)-2,5-Me2C4H2NAlClMe2)ZrMeCl(mu-Cl)](2) (8) and [(eta(5),kappa(1)-2,5-Me2C4H2NAlCl2Et)ZrCl2(mu-Cl)](2) (9), prepared by the reaction of 2 equivalents of ZrCl4, 1 equivalent of 2,5-dimethylpyrrole, and 1 equivalent of aluminum alkyl, showed structures containing a bridging chloride between aluminum and zirconium, thereby giving structural evidence for the lack of catalytic behavior of these complexes. A possible explanation for the moderate or absence of catalytic activity of the aluminum-pyrrolyl complexes was proposed based on DFT calculations.