Synthesis and spectroscopic characterization of group 4 post-metallocenes bearing (σ-aryl)-2-phenolate-6-pyridyl and -isoquinolinyl auxiliaries.

A new series of group 4 bis(benzyl) complexes supported by (σ-aryl)-2-phenolate-6-pyridyl [O,C,N] ligands have been prepared, and all derivatives have been characterized by multinuclear NMR spectroscopy. In the (1)H NMR spectrum of the Ti derivative where [N] = (ortho-F)-substituted isoquinolinyl, one of the two CH2 resonances is observed as a doublet of doublets (collapsing to a normal d upon (19)F-decoupling), whereas the [(1)H,(19)F]-HMQC correlation spectrum reveals a strong crosspeak for this dd resonance only, thus indicating the presence of intramolecular C-HF-C interactions. [(1)H,(19)F]-HMBC experiments have been performed which reveal a significant scalar component for this coupling and confirm that the interactions are genuine. The contrasting NMR spectral patterns for the (ortho-F)-pyridyl Hf analogue, which exhibits two sets of non-identical doublet of doublets for the methylene resonances, have been rationalized. The activities of the isoquinolinyl-based Ti-[O,C,N] catalysts for ethylene polymerization are superior to those of pyridyl-based congeners.