Treatment of Ce[N(SiHMe(2))(2)](3)(thf)(2) with the chlorinating agents PhICl(2), Ph(3)CCl or C(2)Cl(6) gave the homoleptic Ce(IV) silylamide Ce[N(SiHMe(2))(2)](4). When performed in the absence of donating (solvent) molecules, the trivalent cluster Ce(5)[N(SiHMe(2))(2)](8)Cl(7) was isolated.

Readily accessible and easy-to-use phenyliodine(III) dichloride, PhICl(2), has been established as an innovative and superior reagent for the one-electron oxidation of cerium(III) complexes, comprising amide, amidinate, and cyclopentadienyl derivatives. Its use allowed the successful synthesis and structural characterization of the first members of three new classes of chloro-functionalized (organo)cerium(IV) compounds, including the long sought-after Cp(3)CeCl.

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The reactions of the aromatic ketones benzophenone and 9‐fluorenone with trivalent [LnL3] complexes [Ln = Ce, Pr; L = N(SiMe3)2, C5H5 (Cp)] produce highly colored solutions in toluene. Characterization of these complexes by X‐ray diffraction revealed them to be monoadducts of the form [LnL3(ketone)]. The crystallographically determined C–O bonds of these complexes are longer than those of the free ketones. Significant ligand‐to‐metal charge transfer is also indicated by the ν(C=O) vibration of the coordinated ketone, which appears at lower wavelength. Solution‐based 1H NMR spectroscopy showed paramagnetic spectra of complexes Ln[N(SiMe3)2]3(ketone) and Ln(C5H5)3(ketone), which further supports this finding.