The synthesis, spectral characterization, and crystal structure determination of novel lanthanoid porphyrins, i.e., cerium(IV) bis(octaethylporphyrinate) (Ce(OEP)2) and dicerium(III) tris(octaethylporphyrinate) (Ce2(OEP)3), are described. Synthesis is achieved by prolonged boiling of cerium(III) acetylacetonate (Ce(acac)3) and octaethylporphyrin (H2(OEP)) in

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In der Tat gelingt die Oxidation priiparativ durch Umsetzung der Ce'"-Doppeldecker Ce(TTP)2 rnit dem Hexachloroantimonat des Phenoxathiin-Radikalkation~~'] in 1,2-Dichlorethan (DCE) gemllj Gleichung (c):

Q VCH Verlagsgeseiischaji mbH, 0-6940 Weinheim, 1986 0570-0833/86/0303-0287 $ OZ.ZO/O

The preparation of sandwich-type praseodymium-bis(octaethylporphyrinate) systems [Pr(OEP)2]n with different charges -1 ≤ n ≤+1 is described. The following derivatives have been isolated: Praseodymium(III)-hydrogen-bis(octaethylporphyrinate). PrH(OEP)2** (1; n = -1 ) . bis(octaethylporphyrinato)praseodymium(III), Pr(OEP)2 (2; n = 0). and bis(octaethylporphyrinato) praseodymium(III) diiodoaurate(I), [Pr(OEP)2][AuI2] (3; n = +1). For n = 0 or +1, one or both of the porphyrin π-electron systems have defect electrons. The compounds are identified by UV/VIS/NIR, IR and 1H NMR spectra. The cyclic voltammetry data of the "mixed valence' species Pr(OEP)2 in N.N-dimethylformamide are interpreted in terms of three reversible electron transfer processes. The behaviour of PrH(OEP)2 is complicated by a deprotonation occurring during the electrochemical experiment.