High-valent oxoiron(iv) porphyrin p-cation radicals 2 are generally accepted to be the key reactive intermediates in a variety of oxidation reactions by heme-containing enzymes such as cytochromes P450, peroxidases, and catalases.[1,2] Extensive studies with synthetic iron(iii) porphyrin complexes and various terminal oxidants have shown that 2 is generated by heterolytic O X bond cleavage of [...

Simultaneous determination of FeII and FeIII mixtures by spectrophotometric methods is a difficult problem in analytical chemistry because of spectral interferences. By multivariate calibration methods, such as partial least squares (PLS), it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. The method is based on developing the re...

A novel series of mixed-valent, heteroleptic transition metal diketonates that can be utilized as prospective single-source precursors for the low-temperature preparation of oxide materials are reported. The first mixed-valent iron β-diketonates with different FeIII/FeII ratios have been synthesized by applying the mixed-ligand approach. Based on nearly quantitative reaction yields and analysis...

The photocatalytic CO2 reduction into value-added chemicals is regarded as one promising technology to mitigate environmental issues and the energy crisis of modern world due extended emissions. Recent advances have shown that iron porphyrins are considered most efficient molecular catalysts in activation molecules like CO2. Thus, a suitably modified FeIII porphyrin ([FeIII(TF4TMAP)](CF3SO3)5) ...

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(III)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxyg...

A versatile, fast, and nature-inspired polyphenol chemistry surface modification was applied to prepare superhydrophobic surfaces with micro-grooved structures in this study. Tannic acid and iron ion (TA–FeIII) complexes were employed as a molecular building block for anchoring biomimetic coating onto the wood substrate with catalytically reducing formative Ag ions as the rough surface to ensur...

Six new mononuclear [FeIII(LBr,Cl)X]-complexes (LBr,Cl is the dianionic penta-N3O2-dentate Schiff base ligand N,N?-bis(2’-hydroxy-3-bromo-5-chlorobenzylidene)-1,6-diamino-3-azahexane; X: Cl?, N3?, NCO?, NCS?, NCSe?, CN?) were synthesized and their structures, magnetic electrochemical properties studied. Structure analysis measurements showed that [FeIII(LBr,Cl)CN] in low spin state other five c...

FeIII(μ-OH)ZnII Complex that Mimics the Structural and Functional Properties of Purple Acid Phosphatases Ademir Neves,*,† Mauricio Lanznaster,† Adailton J. Bortoluzzi,† Rosely A. Peralta,† Annelise Casellato,†,§ Eduardo Ernesto Castellano,‡ Paul Herrald,§ Mark J. Riley,§ and Gerhard Schenk§ LABINC, Departamento de Quı́mica, UniVersidade Federal de Santa Catarina, 88040-900 Florianópolis, SC, Bra...

Few families of compounds have been as intensely studied as iron porphyrin complexes. In spite of this, a truly four-coordinate Fe(III) porphyrin cation has never before been reported.1 The exceptional electrophilicity of the four-coordinate [FeIII(Porph)]+ cation will even coordinate arene solvent upon crystallization if the counteranion is extremely non-coordinating, as in the work of Reed wi...