Unusual reactivity: A novel unsymmetric dicopper complex gives rise to the species 1-O2 having a μ-η1:η1-O2 binding mode and reactivity patterns not previously observed for symmetric analogues. It is unreactive in oxygen atom transfer reactions, but it can selectively bind phenolate mediate its ortho hydroxylation, thereby demonstrating conceptually different tyrosinase model with exquisite selectivity. Detailed facts of importance specialist readers are published as "Supporting...

Terminal high-valent metal-oxygen species are key reaction intermediates in the catalytic cycle of both enzymes (e.g., oxygenases) and synthetic oxidation catalysts. While tremendous efforts have been directed toward characterization biologically relevant terminal manganese-oxygen iron-oxygen species, corresponding analogues based on late-transition metals such as cobalt, nickel or copper relatively scarce. This scarcity is part related to "Oxo Wall" concept, which predicts that late...

The nature of the oxidizing species in water oxidation reactions with chemical oxidants catalyzed by α-[Fe(OTf)2(mcp)] (1α; mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine, OTf trifluoromethanesulfonate anion) and β-[Fe(OTf)2(mcp)] (1β) has been investigated. Mössbauer spectroscopy provides definitive evidence that 1α 1β generate oxoiron(IV) as resting state. Decomposition paths catalysts have investigated identifying quantifying ligand fragments form upon...

The selective annulation reaction of alkynes with substrates containing inert C-H bonds using cobalt as catalyst is currently a topic attracting significant interest. Unfortunately, the mechanism this transformation still relatively poorly understood, little experimental evidence for intermediates, although an organometallic Co(III) species generally implicated. Herein, we describe rare example preparation and characterization benchtop-stable aryl-Co(III) compounds (NMR, HRMS, XAS, XRD)...

This work directly compares the spectroscopic and reactivity properties of an oxoiron(IV) oxoiron(V) complex that are supported by same neutral tetradentate N-based PyNMe3 ligand. A complete characterization species (2) reveals this compound exists as a mixture two isomers. The thermodynamically more stable isomer (2b) is compared to exhibited previously reported 1e–-oxidized analogue [FeV(O)(OAc)(PyNMe3)]2+ (3). Our data indicates 2b 4 5 orders magnitude slower than 3 in hydrogen atom...

Iron complex [FeIII(N3)(MePy2tacn)](PF6)2 (1), containing a neutral triazacyclononane-based pentadentate ligand, and terminally bound azide ligand has been prepared spectroscopically structurally characterized. Structural details, magnetic susceptibility data, Mössbauer spectra demonstrate that 1 low-spin (S = 1/2) ferric center. X-ray diffraction analysis of reveals remarkably short Fe–N (1.859 Å) long FeN–N2 (1.246 distances, while the FT-IR show an unusually low N–N stretching frequency...

Despite being an indispensable medium for life and the environment, deterioration of water quality continues to be a matter great concern scientific community since this problem has generated need develop processes treatment. Among wide variety types contaminants, presence contaminants emerging (CECs) become issue global concern, they are present in low concentrations can persist bioaccumulate toxic human health aquatic biota. CECs, review focuses on pharmaceutical removal; what favorable...

The integration of clean energy generation with wastewater treatment holds promise for addressing both environmental and concerns. Focusing on photocatalytic hydrogen production treatment, this study introduces PdIn/TiO2 catalysts the simultaneous removal pharmaceutical contaminant paracetamol (PTM) production. Physicochemical characterization showed a high distribution Pd In support as well interaction it. deposition enhance light absorption capability significantly improve evolution...

Abstract The synthesis and characterization of new copper complexes the tetrapyridyl ligand N , N′ ‐di(pyridin‐2‐yl)‐2,2′‐bipyridine‐6,6′‐diamine (bapbpy) is reported. crystal structures compounds [Cu(bapbpy)(H 2 O)]Cl · H O ( 1 ), O)]Br ) O)](NO 3 have been elucidated show copper(II) ions to be in a distorted square‐pyramidal geometry with tetradentate equatorial plane. Conductivity measurements on revealed that it fully ionized methanol, i.e., chloride are not coordinated methanolic...

Octahedral iron(<sc>iv</sc>) tosylimido complexes based in the tacn ligand scaffold exhibit single electron oxidation reactivity.

Playing into our hands: The achiral bipyridine amino acid fluorenylmethyloxycarbonyl 5-amino-3-oxapentanoic (Fmoc-O1PenBpy-OH) has been used for the solid-phase synthesis of metallopeptides. Circular dichroism, molecular modeling, and NMR spectroscopic studies show that chirality resulting metal complexes in aqueous solution is determined, can thus be controlled, by stereochemistry one proline residue loop between two coordinating O1PenBpy residues. Detailed facts importance to specialist...

A flexible and versatile synthetic approach for the construction of water-stable DNA-binding chiral peptide helicates based on solid phase synthesis (SPPS) methodology is reported.

Ungewöhnliche Reaktivität: Ein neuartiger nichtsymmetrischer Dikupferkomplex liefert die unsymmetrische Verbindung 1 O2 mit einer μ-η1:η1-O2-Koordination, deren Reaktivitätsmuster sich von dem symmetrischer Analoga unterscheidet: Sie fungiert nicht als Sauerstoffatomüberträger, bindet aber Phenolat selektiv und vermittelt dessen ortho-Hydroxylierung, was sie zu einem konzeptionell verschiedenen Tyrosinasemodell ausgezeichneter Selektivität macht.

The integration of clean energy generation with wastewater treatment holds promise for addressing both environmental and concerns. Focusing on photocatalytic hydrogen production treatment, the study introduces PdIn/TiO2 catalysts simultaneous removal pharmaceutical contaminant paracetamol production. Physicochemical characterization showed a high distribution Pd In support as well interaction it. deposition enhances light absorption capability significantly improved HER in comparison to TiO2...

The power of two: μ-η2:η2-Peroxodicopper(II) complexes with hexadentate diaminotetrabenzimidazole ligands can catalyze the sulfoxidation aromatic sulfides by a direct oxygen-transfer mechanism (see scheme) in presence sacrificial co-substrate, similarly to enzyme tyrosinase. yields and turnover numbers depend on sulfide co-substrate concentrations electron density S atom.

We demonstrate the application of solid-phase peptide synthesis methods for assembling polynuclear Ir(<sc>iii</sc>) organometallopeptides that exhibit high DNA-binding affinity, sequence selectivity, and cytotoxic effect towards a set cancer cell lines.

The complex α-[Fe(mcp)(OTf)2] (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-diamine and OTf trifluoromethanesulfonate anion) was reported in 2011 by some of us as an active water oxidation (WO) catalyst the presence sacrificial oxidants. However, because chemical oxidants are likely to take part reaction mechanism, mechanistic electrochemical studies critical establishing what extent previous with reagents have actually been meaningful. In this study, its analogues were...

Abstract A new bipyridine building block has been used for the solid‐phase synthesis of dinuclear DNA‐binding ruthenium(II) metallopeptides. Detailed spectroscopic studies suggest that these compounds bind to DNA by insertion into minor groove. Moreover, potential peptide approach is demonstrated straightforward an octaarginine derivative shows effective cellular internalization and cytotoxicity linked with strong interaction, as evidenced steady‐state fluorescence spectroscopy AFM studies.

A series of oligoarginine peptide derivatives containing cyclometallated iridium(<sc>iii</sc>) units display remarkable cytotoxicity, comparable to that cisplatin.

We report and analyze chemoselectivity in the gas phase reactions of cycloalkenes (cyclohexene, cycloheptene, cis-cyclooctene, 1,4-cyclohexadiene) with a non-heme iron(IV)-oxo complex [(PyTACN)Fe(O)(Cl)]+, which models active species iron-dependent halogenases. Unlike halogenases, we did not observe any chlorination substrate. However, observed two other reaction pathways: allylic hydrogen atom transfer (HAT) alkene epoxidation. The HAT is clearly preferred case 1,4-cyclohexadiene, both...

The development of nanoribbon-like structures is an effective strategy to harness the potential benefits graphenic materials due their excellent electrical properties, advantageous edge sites, rapid electron transport, and large specific area. Herein, parallel connected magnetic nanostructured nanoribbons are obtained through synthesis reduced graphene oxide (rGO) using NiCl2 as a precursor with applications in nascent electronic devices. Several analytical techniques have been used for...

Abstract A mild copper‐mediated halogenation reaction of phenolic rings is reported. The bis(2‐hydroxybenzyl)‐1,3‐diaminopropane (H 2 bhbd) with copper(II) chloride in acetonitrile generates linear trinuclear [Cu 3 (bhcbd) Cl ](CH CN), containing modified ligands, whose phenol moieties are selectively chlorinated at the 5‐position. Under comparable experimental conditions bromide, bromination ligand observed, albeit a slower rate. In presence trialkylorthoformates, which used as dehydrating...