ansa-Cyclopentadienyl-Arene Tantalum Complexes: Structure and Reactivity of Neutral, Cationic, and Dicationic Derivatives

Edwin Otten*, Auke Meetsma, Bart Hessen

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

2 Citations (Scopus)

Abstract

The cationic tantalum complex {[eta(6)-Ar-CMe2-eta(5)-C5H4]TaPr}[B(C6F5)(4)] (1; Ar = 3,5-Me2C6H3) serves as a starting material for a series of neutral, monocationic, and dicationic derivatives. The cationic hydride {[eta(6)-Ar-CMe2-eta(5)-C5H4]TaH}[B(C6F5)(4)] (2) that results from hydrogenolysis of 1 inserts the di- and trisubstituted olefins cyclopentene and 2-methyl-2-pentene; it reacts with styrene to give the 2,1-insertion product, for which the Ta-CH(Me)Ph group is bound in a sigma(3)-allylic fashion. A neutral complex is obtained from 1 by reaction with Br-, and a dicationic derivative is available by hydride abstraction from 2 using the Lewis acidic trityl cation. All compounds described here retain the unusual ansa-(eta(5)-cyclopentradienyl,eta(6)-arene) coordination mode of the ligand that stabilizes the formally Ta(III) center. X-ray structures and DFT calculations show that the metal-arene interaction contains a significant pi back-donation component (arene

Original languageEnglish
Pages (from-to)6071-6079
Number of pages9
JournalOrganometallics
Volume31
Issue number17
DOIs
Publication statusPublished - 10-Sep-2012

Keywords

  • ACTIVE LIGAND COMPLEX
  • SEPARATED ION-PAIRS
  • TRANSITION-METAL
  • POLYMERIZATION CATALYSTS
  • CYCLOADDITION REACTIONS
  • ABSOLUTE-CONFIGURATION
  • ETHYLENE TRIMERIZATION
  • ETHENE TRIMERIZATION
  • MOLECULAR-STRUCTURE
  • CRYSTAL-STRUCTURE

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