The complex Cp3Ce(O-i-Pr) (Cp = .eta.5-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. Eiectronic structure calculations at the nonrelativistic Xa-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.
Efficient synthesis, redox characteristics, and electronic structure of a tetravalent tris(cyclopentadienyl)cerium alkoxide complex
CASARIN, MAURIZIO;
1988
Abstract
The complex Cp3Ce(O-i-Pr) (Cp = .eta.5-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. Eiectronic structure calculations at the nonrelativistic Xa-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.Pubblicazioni consigliate
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