Abstract
The complex Cp3Ce(O-i-Pr) (Cp = η5-C5H6) 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 language | English (US) |
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Pages (from-to) | 2360-2364 |
Number of pages | 5 |
Journal | Organometallics |
Volume | 7 |
Issue number | 11 |
DOIs | |
State | Published - Nov 1988 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry