Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. Probing the limits of anion `noncoordination` via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study

Journal Article · Tue Mar 04 04:00:00 EST 1997 · Organometallics

DOI:https://doi.org/10.1021/om960880j· OSTI ID:484470

Jia, L; Yang, X; Stern, C L; Marks, T J ^[1]

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1. Northwestern Univ., Evanston, IL (United States)

The silyl-functionalized/protected derivatives of the tetrakis(perfluoroaryl)borate anions, B(C{sub 6}F{sub 4}TBS){sub 4}{sup -} and B(C{sub 6}F{sub 4}TIPS){sub 4}{sup -} (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) have been synthesized, and a series of stable, highly reactive Zr and Th ion-paired methyl and hydride catalysts have been isolated using these anions. In contrast, the analogous B(C{sub 6}F{sub 5}){sub 4}{sup -}-based zirconocene methyl complexes are not stable at room temperature; however, B(C{sub 6}F{sub 5}){sub 4}{sup -}-based zirconocene hydride complexes can be isolated. The relative coordinative ability of the series of fluoroarylborates with respect to metallocene cations has been evaluated on the basis of spectroscopic and reactivity data. The polymerization activity of the zirconocene catalysts reaches a maximum when B(C{sub 6}F{sub 4}TBS){sub 4}{sup -} and B(C{sub 6}F{sub 4}TIPS){sub 4}{sup -} are counteranions, and the polymerization activity of the Zr constrained geometry catalyst reaches a maximum in aromatic solvents due to arene coordination when B(C{sub 6}F{sub 5}){sub 4}{sup -} is the counteranion. 37 refs., 5 figs., 7 tabs.

• DOE Contract Number: FG02-86ER13511
• OSTI ID: 484470
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 16; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
ALKENES
ANIONS
CATALYSIS
CATIONS
CHEMICAL BONDS
CRYSTAL STRUCTURE
LIGANDS
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
POLYMERIZATION
SOLUTIONS
STABILITY
SYNTHESIS
THORIUM
X-RAY DIFFRACTION
ZIRCONIUM