Victor A. Adamian

Electrochemical and Spectral Characterization of Iron Corroles in High and Low Oxidation States: First Structural Characterization of an Iron(IV) Tetrapyrrole π Cation Radical

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)FeIV(C6H5), (OEC)FeIVCl, and (OEC)FeIII(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)FeIV(C6H5) and (OEC)FeIVCl to their iron(III) forms upon a one-electron reduction and to iron(IV) corrole π cation radicals upon a one-electron oxidation. The metal center in [(OEC)FeIII(C6H5)]- is low spin (S = 1/2) as compared to electrogenerated [(OEC)FeIIICl]-, which contains an intermediate-spin (S = 3/2) iron(III). (OEC)FeIII(py) also contains an intermediate-spin-state iron(III) and, unlike previously characterized (OEC)FeIII(NO), is converted to an iron(IV) corrole upon oxidation rather than to an iron(III) π cation radical. Singly oxidized [(OEC)FeIV(C6H5)]•+ is the first iron(IV) tetrapyrrole π cation radical to be isolated and was structurally characterized as a perchlorate salt. It crystallizes in the triclinic space group P1̄ with a = 10.783(3) Å, b = 13.826(3) Å, c = 14.151(3) Å, α = 78.95(2)°, β = 89.59(2)°, and γ = 72.98(2)° at 293 K with Z = 2. Refinement of 8400 reflections and 670 parameters against F o2 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.

Metallomacrocycles with metalmetal bonds: synthesis, characterization and electrochemistry of [(P)SnRe(CO)5]BF4 and [{(P)Sn}2Re(CO)4]BF4 derivatives, where P = tetra-p-tolyporphyrin or tetra-m-tolylporphyrin

Abstract The synthesis and characterization of bimetallic and trimetallic porphyrins of the type [(P)SnRe(CO) 5 ]BF 4 and [{(P)Sn} 2 Re(CO) 4 ]BF 4 are reported where P is the dianion of tetra- p -tolyporphyrin (TpTP) or tetra- m -tolyporphyrin (TmTP). These metal-metal bonded complexes were synthesized by reaction of Re 2 (CO) 10 with the corresponding (P)SnCl 2 derivatives in 1,2-dichlorobenzene followed by a reaction with NaBF 4 or TBABF 4 in toluene to give the BF − 4 salt. Each compound was characterized by a variety of spectroscopic and electrochemical techniques while the structures were assigned on the basis of FAB mass spectral data and by comparison of their physicochemical properties with data for related metalmetal bonded porphyrins previously synthesized in our laboratories. Each [(P)SnRe(CO) 5 ]BF 4 complex undergoes two reversible one-electron reductions at the porphyrin π-ring system while each [{(P)Sn} 2 Re(CO) 4 ]BF 4 derivatives exhibits four reversible reductions in accordance with the presence of two Sn porphyrin units having interacting redox centers. These reductions also occur at the conjugated macrocycle. The first oxidation of each compound is irreversible and is associated with a cleavage of the tinrhenium bond.