A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality

Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)(3)/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg g(Cr)(-1) h(-1)) and C-8 olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C-6 + 1-C-8) selectivities, exceeding 90 wt%, as a result of high 1-C-6 purity (>90 wt%) in the C-6 fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C-6 cyclics controlled highly alpha-selective ethylene oligomerization.