Replacement of Volatile Acetic Acid by Solid SiO2@COOH Silica (Nano)Beads for (Ep)Oxidation Using Mn and Fe Complexes Containing BPMEN Ligand

Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CH3COOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by SiO2 (nano)particles with two different sizes to which pending carboxylic functions were added (SiO2@COOH). The SiO2@COOH beads were obtained by the functionalization of SiO2 with pending nitrile functions (SiO2@CN) followed by CN hydrolysis. All complexes and silica beads were characterized by NMR, infrared, DLS, TEM, X-ray diffraction. The replacement of CH3COOH by SiO2@COOH (100 times less on molar ratio) has been evaluated for (ep)oxidation on several substrates (cyclooctene, cyclohexene, cyclohexanol) and discussed in terms of activity and green metrics.

Study of the Effect of Absorbed Cu Species on the Surface of Specularite (0 0 1) by the DFT Calculations

Cu2+ exhibited a good activation effect on specularite. However, its microscopic activation mechanism needs further study. Additionally, Cu2+ was mainly present in the flotation solution as Cu2+, Cu(OH)+, and Cu(OH)2 at pH = 7. Therefore, density functional theory (DFT) calculations were used to investigate the effect of Cu species such as Cu2+, Cu(OH)+, and Cu(OH)2 adsorbed on the crystal structure and properties of the specularite (0 0 1) surface. The adsorption mechanism of different Cu components on the surface was also further clarified by the analyses of the adsorption model, adsorption energy, partial density of states (PDOS), charge transfer, and bond properties. In addition, the obtained results are discussed. Based on the obtained results, it can be concluded that the geometric structure and electronic properties on the surface changed after adsorbing Cu components and that the O3–Fe1–O1 structure was more susceptible to the adsorbates. The adsorption engines results show that Cu components could be spontaneously adsorbed onto the specularite (0 0 1) surface with adsorption energies of −0.76, −0.85, and −1.78 eV, corresponding to Cu2+, CuOH+, and Cu(OH)2, respectively. Therefore, the adsorption stability of the Cu species on the specularite surface increased in the order of Cu2+ < Cu(OH)+ < Cu(OH)2. Additionally, the adsorption sites for Cu species on the surface were different. Cu2+ interacted mainly with O atoms on the surface, forming Cu–O complexes, while Cu(OH)+ and Cu(OH)2 acted mainly through the O atom of –OH, interacting with Fe atoms to form Cu–O–Fe complexes. The formation of Cu–O and Cu–O–Fe complexes increased the adsorption sites for sodium oleate, with more hydrophobic species being generated to improve the floatability of specularite.

Biological Inspirations: Iron Complexes Mimicking the Catechol Dioxygenases

Within the broad group of Fe non-heme oxidases, our attention was focused on the catechol 1,2- and 2,3-dioxygenases, which catalyze the oxidative cleavage of aromatic rings. A large group of Fe complexes with N/O ligands, ranging from N3 to N2O2S, was developed to mimic the activity of these enzymes. The Fe complexes discussed in this work can mimic the intradiol/extradiol catechol dioxygenase reaction mechanism. Electronic effects of the substituents in the ligand affect the Lewis acidity of the Fe center, increasing the ability to activate dioxygen and enhancing the catalytic activity of the discussed biomimetic complexes. The ligand architecture, the geometric isomers of the complexes, and the substituent steric effects significantly affect the ability to bind the substrate in a monodentate and bidentate manner. The substrate binding mode determines the preferred mechanism and, consequently, the main conversion products. The preferred mechanism of action can also be affected by the solvents and their ability to form the stable complexes with the Fe center. The electrostatic interactions of micellar media, similar to SDS, also control the intradiol/extradiol mechanisms of the catechol conversion by discussed biomimetics.

Electrodeposition of Fe-Complexes on Oxide Surfaces for Efficient OER Catalysis

Progress in non-covalent/self-assembled immobilization methods on (photo)electrode materials for molecular catalysts could broaden the scope of attainable systems. While covalent linkage (though considered more stable) necessitates functional groups introduced by means of often cumbersome synthetic procedures, non-covalent assemblies require sufficient propensity of the molecular unit for surface adsorption, thus set less rigorous pre-requisites. Herein, we report efficient electrodeposition (ED) of two Fe(III) complexes prepared with closely related NN’N pincer ligands yielding stable and active ad-layers for the electrocatalysis of the oxygen-evolving reaction (OER). The ED method is based on the utilization of a chloride precursor complex [FeIIICl2(NN’N)], which is dissolved in an organic electrolyte undergoes chloride/aqua ligand exchange upon addition of water. ED provides patchy distribution of a chloride-depleted catalyst layer on indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) surfaces, which can be applied for long periods as OER electrocatalysts. Compared to drop-casting or layering of [FeIIICl2(NN’N)] with Nafion (a commonly used support for molecular electrocatalysts), the surface modification by ED is a material saving and efficient method to immobilize catalysts.

The Esterase PfeE, the Achilles’ Heel in the Battle for Iron between Pseudomonas aeruginosa and Escherichia coli

Bacteria access iron, a key nutrient, by producing siderophores or using siderophores produced by other microorganisms. The pathogen Pseudomonas aeruginosa produces two siderophores but is also able to pirate enterobactin (ENT), the siderophore produced by Escherichia coli. ENT-Fe complexes are imported across the outer membrane of P. aeruginosa by the two outer membrane transporters PfeA and PirA. Iron is released from ENT in the P. aeruginosa periplasm by hydrolysis of ENT by the esterase PfeE. We show here that pfeE gene deletion renders P. aeruginosa unable to grow in the presence of ENT because it is unable to access iron via this siderophore. Two-species co-cultures under iron-restricted conditions show that P. aeruginosa strongly represses the growth of E. coli as long it is able to produce its own siderophores. Both strains are present in similar proportions in the culture as long as the siderophore-deficient P. aeruginosa strain is able to use ENT produced by E. coli to access iron. If pfeE is deleted, E. coli has the upper hand in the culture and P. aeruginosa growth is repressed. Overall, these data show that PfeE is the Achilles’ heel of P. aeruginosa in communities with bacteria producing ENT.

Dinuclear [OSSO]-Fe complexes for the reaction of CO2 with epoxides

A dinuclear iron-based catalytic system, bearing a new alkyl-bridged bis-[OSSO]-type ligand, for the coupling of CO2 with epoxides is reported. Turnover frequency up to 1680 h-1 was recorded for the...

The cysteine residue-bridged dinuclear Ni-Fe complexes related to [NiFe]-H2ases

To develop the biomimetic chemistry of [NiFe]-H2ases, we have synthesized the first cysteine residue-containing [NiFe]-H2ase mimics (diphosphine)Ni[SCH2CH(CO2Me)NHCOC5H4-η5]2Fe (1, diphosphine = Ph2P(CH2)2PPh2; 2, Ph2PCH=CHPPh2; 3, 1,2-(Ph2P)2C6H4; 4, (Ph2P)2NCH2C6H4Me-p; 5, (Ph2P)2NCH2CO2Et; 6,...

Investigation of Iron–Ammine and Amido Complexes within a C3-Symmetrical Phosphinic Amido Tripodal Ligand

The primary and secondary coordination spheres can have large regulatory effects on the properties of metal complexes. To examine their influences on the properties of monomeric Fe complexes, the tripodal...

Precise control of the degree and regioselectivity of functionalization in nitro- and amino-functionalized di(trispyrazolylborato)iron(II) spin crossover complexes

Di(trispyrazolylborato)iron(II) ([Tp2Fe]) complexes represent one of the most robust class of spin crossover complexes. Their stability renders them particularly suitable for integration in nanoscale devices, e.g. as sensors or information...