Angen Chem. Inr Ed. Engl. 25 (1986) No. 3 0 VCH Verlagsgesellschafi mbH. 0-6940 Wernheim, I986 0570-0833/86/0303-0259 $ 02 50/0

Dtw'ilctrtecl to Piofcrc.or Eimt Otto F i~t h e r 017 the> ol c ci\ioi? of h r~ 75th birt~7da1The coordination chemistry of metals in unusual oxidation states is a fascinating aspect of research in the field ofmetalloporphyrins. Of particular significance in this respect are oxoiron porphyrins containing tetravalent iron, since complexes of this sort occur as reactive intermediates in numerous biological and biomimetic oxidation processes."] Iron(iv) porphyrins, in which the metal is not present as part of a [Fe=O] (FRG) phyrinoids corrole["-the aromatic parent substance of corrin. the ring system of vitamin B,, --and iso~orrole['~ may enable the preparation of the corresponding neutral complexes, that is. types 2 and 4, respectively. This supposition appeared to be substantiated all the more so. as it was recently shown that stable iron(iv) complexes with ligands based on pentane-2,4-dione-bis(S-alky1isothiosemicarbazides)-which are also trianionic-could be synthesized.18,9] We have now found that octaethylcorrole 5 can be readily converted into the triad of stable complexes 7-9, all of which contain formally tetravalent iron."'] Furthermore, the existence of the iron corrole 10 (bearing an axial pyridine ligand) with a formal oxidation state of the metal of + 111 was corroborated.

Until very recently the Ni and Cu corroles, already described in the sixties, were regarded as the MII complexes 1 (M = Ni, Cu). Some doubt arose about this interpretation after the existence of FeIV corroles demonstrated that corroles can stabilize metals in unusual oxidation states. Thorough physical studies have now shown that the metal atoms in the Ni and Cu corroles do in fact have the formal oxidation state +III (2).

Angew. Chem. lnt. Ed. Engl. 26 (1987) No. 9 Angen Chem. I n f . Ed. Engl. 26 (1987) No. 9 0 VCH Verlagsgesellschafi mbH. 0-6940 Weinheim. 1987 0570-0833/87/0909-0931 $ 02.50/0

The electrochemistry and spectroscopic properties of three iron corroles were examined in benzonitrile, dichloromethane, and pyridine containing 0.1 M tetra-n-butylammonium perchlorate or tetra-n-ethylammonium hexafluorophosphate as supporting electrolyte. The investigated compounds are represented as (OEC)Fe(IV)(C(6)H(5)), (OEC)Fe(IV)Cl, and (OEC)Fe(III)(py), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. Each iron(IV) corrole undergoes two one-electron reductions and two or three one-electron oxidations depending upon the solvent. Under the same solution conditions, the iron(III) corrole undergoes a single one-electron reduction and one or two one-electron oxidations. Each singly oxidized and singly reduced product was characterized by UV-vis and/or EPR spectroscopy. The data indicate a conversion of (OEC)Fe(IV)(C(6)H(5)) and (OEC)Fe(IV)Cl to their iron(III) forms upon a one-electron reduction and to iron(IV) corrole pi cation radicals upon a one-electron oxidation. The metal center in [(OEC)Fe(III)(C(6)H(5))](-) is low spin (S = (1)/(2)) as compared to electrogenerated [(OEC)Fe(III)Cl](-), which contains an intermediate-spin (S = (3)/(2)) iron(III). (OEC)Fe(III)(py) also contains an intermediate-spin-state iron(III) and, unlike previously characterized (OEC)Fe(III)(NO), is converted to an iron(IV) corrole upon oxidation rather than to an iron(III) pi cation radical. Singly oxidized [(OEC)Fe(IV)(C(6)H(5))](*)(+) is the first iron(IV) tetrapyrrole pi cation radical to be isolated and was structurally characterized as a perchlorate salt. It crystallizes in the triclinic space group P&onemacr; with a = 10.783(3) Å, b = 13.826(3) Å, c = 14.151(3) Å, alpha = 78.95(2) degrees, beta = 89.59(2) degrees, and gamma = 72.98(2) degrees at 293 K with Z = 2. Refinement of 8400 reflections and 670 parameters against F(o)(2) yields R1 = 0.0864 and wR2 = 0.2293. The complex contains a five-coordinated iron with average Fe-N bond lengths of 1.871(3) Å. The formulation of the electron distribution in this compound was confirmed by Mössbauer, X-ray crystallographic, and magnetic susceptibility data as well as by EPR spectroscopy, which gives evidence for strong antiferromagnetic coupling between the iron(IV) center and the singly oxidized corrole macrocycle.