Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 24, Pages 6371-6379Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201705707
Keywords
arylation; cyclic voltammetry; epoxides; kinetics; radicals
Categories
Funding
- Deutsche Forschungsgemeinschaft [SFB 813, Ga 619/12-1]
- Konrad-Adenauer-Stiftung
- Evangelisches Studienwerk Villigst
- Jurgen Manchot Stiftung
- National Science Foundation [CHE-1123815, CHE-1565741]
- Direct For Mathematical & Physical Scien [1565741] Funding Source: National Science Foundation
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We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp2TiX-catalysts that are prepared in situ from readily available Cp2TiX2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp2TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands.
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