Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex

Antonino Gulino, Maurizio Casarin, Vincent P. Conticello, John G. Gaudiello, Heiko Mauermann, Ignazio Fragalá, Tobin J Marks

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

The complex Cp3Ce(O-i-Pr) (Cp = η5-C5H5) can be efficiently prepared from cerium tetrakis(isopropoxide) and Me3SnCp. It is shown to be a genuine Ce(IV) complex by 1H/13C NMR, elemental analysis, and cyclic voltammetry/controlled potential coulometry in Bu4N+BF4-/THF. The latter data indicate that Cp3Ce(O-i-Pr) is a relatively strong oxidizing agent (E1/2 = +0.32 vs SSCE) and that one-electron reduction is both electrochemically and chemically reversible. Electronic structure calculations at the nonrelativistic Xα-DVM level suggest nonnegligible Ce-Cp f orbital covalency and yield transition state ionization energies in good agreement with He I/He II photoelectron spectra. There are substantial differences in redox properties and metal-ligand bonding between Cp3Ce(O-i-Pr) and the other known tetravalent cerium organometallic complex Ce(C8H8)2.

Original languageEnglish
Pages (from-to)2360-2364
Number of pages5
JournalOrganometallics
Volume7
Issue number11
Publication statusPublished - 1988

    Fingerprint

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Gulino, A., Casarin, M., Conticello, V. P., Gaudiello, J. G., Mauermann, H., Fragalá, I., & Marks, T. J. (1988). Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex. Organometallics, 7(11), 2360-2364.