Abstract
By applying a salt metathesis approach between Ce(OtBu3)2(NO3)2(THF)2 and the potassium salts of mono- and ditrimethylsilyl substituted cyclopentadienes, we were able to isolate two new Ce(IV) metallocenes, including to the best of our knowledge, the first structurally characterized bis-cyclopentadiene Ce(IV) compound.
Highlights
Cerium(IV) is a strong one-electron oxidant and its use in areas such as organic synthesis [1,2,3], bioinorganic chemistry [4,5], materials science [6] and industrial catalysts such as automotive catalytic converters [7,8,9,10,11,12,13] is widespread
Cp2Ce(OtBu3)2 and Cp3Ce(OtBu3), the latter being crystallographically characterized [28]. These complexes utilized a soluble Ce(IV) alkoxide nitrate species which is readily prepared from cerium ammonium nitrate (CAN) [18]
The Ce–O bonds were inert to all our attempts to substitute the OtBu ligands, highlighting the oxophilic nature of the lanthanides
Summary
Cerium(IV) is a strong one-electron oxidant and its use in areas such as organic synthesis [1,2,3], bioinorganic chemistry [4,5], materials science [6] and industrial catalysts such as automotive catalytic converters [7,8,9,10,11,12,13] is widespread. Soluble cerium(IV) complexes are important precursors for the preparation of ceria nanoparticles [14] and this has increased the demand for well-characterized precursors for the development of this area. Ce(III) compounds and the use of materials such as Ce(OPri), Ce(OTf), cerium ammonium nitrate (CAN) derived [Ce(OtBu)2(NO3)2(THF)2] [18] and most recently, the amide complex, Ce[(NiPr2)4] [19]. Cp2Ce(OtBu3) and Cp3Ce(OtBu3), the latter being crystallographically characterized [28] These complexes utilized a soluble Ce(IV) alkoxide nitrate species which is readily prepared from cerium ammonium nitrate (CAN) [18]. Following this in 2010, Anwander and Edelmann reported the oxidation of CeCp3 with PhICl2 to form Cp3CeCl [29]. Compound, and we will briefly discuss attempts to perform subsequent transformations of these relatively rare compounds
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