New perfluoroarylborane activators for single-site olefin polymerization. Acidity and cocatalytic properties of a "superacidic" perfluorodiboraanthracene

Matthew V. Metz, David J. Schwartz, Charlotte L. Stern, Tobin J Marks, Peter N. Nickias

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Abstract

The synthesis, Lewis acid properties, and single-site olefin polymerization characteristics of catalyst systems utilizing the binuclear organo-Lewis acid cocatalyst 9, 10-bis(pentafluorophenyl)-9, 10-diboraoctafluoroanthracene, C12F8B2(C6F5)2 (8b), are reported. X-ray diffraction analysis of 8b reveals a nearly planar C12F8B2 core with -C6F5 rings rotated 75° out of the plane, hindering π communication between the pendant -C6F5 substituents and the C12F8B2 core, and thereby enhancing Lewis acidity at the boron centers. Competition equilibration experiments with 8b, B(C6F5)3, and acetonitrile over a wide temperature range demonstrate that 8b is a stronger Lewis acid than B(C6F5)3 by ΔH = +1.4(2) kcal/mol and ΔS = -5.3(1) eu. The diffraction-derived molecular structure of 8b←NCCH3 reveals substantial skeletal reorganization only at the coordinated boron center. When it is paired with dimethyl organo-group 4 catalyst precursors, 8b affords extremely efficient single-site olefin polymerization systems in both laboratory and large-scale reactors. In all cases, 8b forms polymerization systems with higher activities than those utilizing B(C6F5)3 as the cocatalyst.

Original languageEnglish
Pages (from-to)4159-4168
Number of pages10
JournalOrganometallics
Volume21
Issue number20
DOIs
Publication statusPublished - Sep 30 2002

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ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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