title: Iron porphyrin dications with neutral axial ligands: DFT calculations delineate similarities with heme protein compound II intermediates.
abstract: OLYP/TZP calculations on two symmetrized model complexes [Fe(TPP)(py)(2)](2+) and [Fe(TPP)(PhNC)(2)](2+) (TPP = meso-tetraphenylporphyrin, py = pyridine, PhNC = phenylisocyanide) reveal dense manifolds of low-energy electronic states. For the latter complex, broken-symmetry calculations successfully reproduce the unique S = 0 ground state that is expected on the basis of experimental measurements on a closely related complex; the S = 0 state arises from antiferromagnetic coupling between a low-spin d(xy)(1)(d(xz),d(yz))(4) Fe(III) center and a porphyrin "a(2u)" radical. Furthermore, the calculations indicate low-energy Fe(IV) states for both complexes. Overall, the results contribute to our deepening understanding of the factors contributing to the stability of iron(IV) centers. Thus, a dianionic π-donor oxo ligand is no longer deemed a requirement for the stability of heme-based Fe(IV) centers; iron(IV) intermediates of heme proteins such as chloroperoxidase, catalase, and MauG, having only monanionic ligands such as hydroxide, thiolate, and phenolate and/or (in the case of MauG) a neutral histidine as axial ligands, are now firmly established.
authors.affiliation: Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, 9037 Tromsø, Norway.
authors.forename: Adam C
authors.initials: AC
authors.lastname: Chamberlin
authors.forename: Akira
authors.initials: A
authors.lastname: Ikezaki
authors.forename: Mikio
authors.initials: M
authors.lastname: Nakamura
authors.forename: Abhik
authors.initials: A
authors.lastname: Ghosh
mesh_terms: D002374:Catalase / Q000737:chemistry; D002711:Chloride Peroxidase / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D008665:Metalloporphyrins; D011166:Porphyrins; D007501:Iron; D002711:Chloride Peroxidase; D002374:Catalase