A novel phenolate "constrained geometry" catalyst system. Efficient synthesis, structural characterization, and α-olefin polymerization catalysis

You Xian Chen, Peng Fei Fu, Charlotte L. Stern, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

This paper reports the convenient "one-pot" synthesis of a bifunctional -Me4Cp̂ phenolate- ligand and the efficient "one-step" synthesis of the corresponding TiIV and ZrIV complexes. The reaction of 2-bromo-4-methylphenol with 2 equiv of nBuLi followed by addition of 2,3,4,5-tetramethyl-2-cyclopentenone produces the bifunctional mono-Cp phenol ligand precursor 2-(tetramethylcyclopentadienyl)-4-methylphenol ((TCP)H2, 1). Reaction of 1 with Ti(CH2-Ph)4 at 60°C in toluene cleanly generates (TCP)Ti(CH2Ph)2 (2), while the corresponding reaction with Zr(CH2Ph)4 at higher temperatures affords the chelated C2-symmetric zirconocene (TCP)2Zr (3). In solution at room temperature, the two benzyl groups of 2 are magnetically equivalent, however, in the solid state, X-ray diffraction reveals that one benzyl group is coordinated in a normal η1-fashion and the other in an η2-mode. The small Cp-(centroid)-Ti-O angle of 107.7(2)° in 2 indicates sterically open features in common with amido-based "constrained geometry" polymerization catalysts. Low-temperature NMR-scale reactions of 2 with B(C6F5)3 and Ph3C+B(C6F5)4- indicate the formation of the corresponding cationic complexes (TCP)TiCH2Ph+ PhCH2B(C6F5)3- (4) and (TCP)TiCH2Ph+B(C6F5) 4- (5). Upon activation with Ph3C+B(C6F5)4 -, complex 2 is highly active for ethylene, propylene, and styrene polymerization.

Original languageEnglish
Pages (from-to)5958-5963
Number of pages6
JournalOrganometallics
Volume16
Issue number26
Publication statusPublished - Dec 23 1997

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Alkenes
Catalysis
alkenes
catalysis
polymerization
Polymerization
catalysts
Catalysts
Geometry
synthesis
geometry
ligands
propylene
styrenes
phenols
centroids
Ligands
toluene
Styrene
ethylene

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

A novel phenolate "constrained geometry" catalyst system. Efficient synthesis, structural characterization, and α-olefin polymerization catalysis. / Chen, You Xian; Fu, Peng Fei; Stern, Charlotte L.; Marks, Tobin J.

In: Organometallics, Vol. 16, No. 26, 23.12.1997, p. 5958-5963.

Research output: Contribution to journalArticle

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abstract = "This paper reports the convenient {"}one-pot{"} synthesis of a bifunctional -Me4Cp̂ phenolate- ligand and the efficient {"}one-step{"} synthesis of the corresponding TiIV and ZrIV complexes. The reaction of 2-bromo-4-methylphenol with 2 equiv of nBuLi followed by addition of 2,3,4,5-tetramethyl-2-cyclopentenone produces the bifunctional mono-Cp phenol ligand precursor 2-(tetramethylcyclopentadienyl)-4-methylphenol ((TCP)H2, 1). Reaction of 1 with Ti(CH2-Ph)4 at 60°C in toluene cleanly generates (TCP)Ti(CH2Ph)2 (2), while the corresponding reaction with Zr(CH2Ph)4 at higher temperatures affords the chelated C2-symmetric zirconocene (TCP)2Zr (3). In solution at room temperature, the two benzyl groups of 2 are magnetically equivalent, however, in the solid state, X-ray diffraction reveals that one benzyl group is coordinated in a normal η1-fashion and the other in an η2-mode. The small Cp-(centroid)-Ti-O angle of 107.7(2)° in 2 indicates sterically open features in common with amido-based {"}constrained geometry{"} polymerization catalysts. Low-temperature NMR-scale reactions of 2 with B(C6F5)3 and Ph3C+B(C6F5)4- indicate the formation of the corresponding cationic complexes (TCP)TiCH2Ph+ PhCH2B(C6F5)3- (4) and (TCP)TiCH2Ph+B(C6F5) 4- (5). Upon activation with Ph3C+B(C6F5)4 -, complex 2 is highly active for ethylene, propylene, and styrene polymerization.",
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