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High‐temperature catalysts for the production of α‐olefins based on iron(II) and iron(III) tridentate bis(imino)pyridine complexes modified by nitrilo group
Authors:Alex S Ionkin  William J Marshall  Douglas J Adelman  Barbara Bobik Fones  Brian M Fish  Matthew F Schiffhauer  Paul D Soper  Robert L Waterland  Rupert E Spence  Tuyu Xie
Institution:1. DuPont Central Research and Development, Experimental Station, Wilmington, Delaware 19880‐0328;2. E. I. du Pont Canada Company, Research and Development Center, Kingston, Ontario, Canada K7L 5A5
Abstract:Series of Fe(II) and Fe(III) tridentate bis(imino)pyridine complexes without nitrilo groups 2–6 and with nitrilo groups 7–13 were synthesized. According to X‐ray analysis, the introduction of nitrilo groups in para‐ and ortho‐positions tends to result in shorter axial Fe? N bonds. Both types of complexes, 2–6 and 9–13 , afforded very productive catalysts for the production of α‐olefins with higher K values and better linearity of Schultz–Flory distribution α‐olefins than the parent methyl substituted Fe(II) complex 1 . Noticeably, the complexes functionalized with a para‐nitrilo group 9–13 tend to make α‐olefins with higher K values of the Schultz–Flory distribution, more ideal distributions, and less of the heavier insoluble fractions of α‐olefins than corresponding nonsymmetrically substituted complexes without para‐nitrilo groups 2–6 . Statistically significant correlations were obtained between % solids of total α‐olefins and the blocked solid angle fraction in the +z hemisphere ( equation image = 51.3%, p = 0.012) and between catalyst productivity and total blocked solid angle fraction (equation image = 43.5%, p = 0.023). The modest values of equation image show that, while steric effects are significant, they are not the sole factor determining catalyst performance. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 585–611, 2008
Keywords:bis(imino)pyridine ligands  crystal structures  iron  oligomers  organometallic catalysts  synthesis  transition metal chemistry
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