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Abstract The preparation of the lanthanoid bisporphinates, bis[meso-tetra(p-tolyl)porphinato]-cerium(IV) [Ce(TTP)2**] and bis[meso-tetra(p-tolyl)porphinato]hydrogenpraseodymium-(III) [PrH(TTP)2] from Ce(acac)3 and Pr(acac)3 in boiling 1,2,4-trichlorobenzene is described. Ce(TTP)2 is a diamagnetic and rather inert CeIV derivative, PrH(TTP)2 is a paramagnetic PrIII complex and may be deprotonated to give the anion [Pr(TTP)2]- which is characterized by conductivity measurements, electrophoresis, and isolation of its tetra(n-butyl)ammonium or tetraphenylarsonium salt. The compounds are identified by UV/VIS, IR, 1H NMR, and mass spectra. The data are consistent with a sandwich-type square antiprismatic array of the two porphinate disks about the CeIV or PrIII ion as found earlier in the bis-phthalocyaninates U(Pc)2 or NdH(Pc)2.

Mononuclear hydroxoiron(il1) porphyrins are normally unstable, the ease of condensation of isolated FeOH groups to FeOFe bridges preventing their isolationr2I. Recently, a variety of mononucIear hydroxohemins have been mentioned, the stability of which is attributed to bifacial steric hindrance, i. e. to bulky substituents on both sides of the porphinatoThe published data of these compounds d o not yet allow full characterization.We report here a well-defined mononuclear hydroxoiron(rr1) complex of a porphinoid ligand system: [a,y-The synthesis of 1 is achieved by reductive tert-butylation of octaethylporphinatozinc, demetalation of the product, iron insertion, and exhaustive chromatography on alumina by analogy to (for details see I6'l).

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