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

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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

Cerium
alkoxides
cerium
Electronic structure
Digital voltmeters
coulometry
Coulometers
electronic structure
Ionization potential
Organometallics
synthesis
Photoelectrons
Oxidants
Cyclic voltammetry
photoelectrons
Metals
Nuclear magnetic resonance
Ligands
ionization
orbitals

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.

Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex. / Gulino, Antonino; Casarin, Maurizio; Conticello, Vincent P.; Gaudiello, John G.; Mauermann, Heiko; Fragalá, Ignazio; Marks, Tobin J.

In: Organometallics, Vol. 7, No. 11, 1988, p. 2360-2364.

Research output: Contribution to journalArticle

Gulino, A, Casarin, M, Conticello, VP, Gaudiello, JG, Mauermann, H, Fragalá, I & Marks, TJ 1988, 'Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex', Organometallics, vol. 7, no. 11, pp. 2360-2364.
Gulino A, Casarin M, Conticello VP, Gaudiello JG, Mauermann H, Fragalá I et al. Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex. Organometallics. 1988;7(11):2360-2364.
Gulino, Antonino ; Casarin, Maurizio ; Conticello, Vincent P. ; Gaudiello, John G. ; Mauermann, Heiko ; Fragalá, Ignazio ; Marks, Tobin J. / Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex. In: Organometallics. 1988 ; Vol. 7, No. 11. pp. 2360-2364.
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