A5003430775- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Metal-Catalyzed Oxygenation Mechanisms
- Porphyrin and Phthalocyanine Chemistry
- Metal complexes synthesis and properties
- Magnetism in coordination complexes
- Polyoxometalates: Synthesis and Applications
- Asymmetric Synthesis and Catalysis
- Photosynthetic Processes and Mechanisms
- Covalent Organic Framework Applications
- Coordination Chemistry and Organometallics
- Hemoglobin structure and function
- CO2 Reduction Techniques and Catalysts
- Graphene research and applications
- Chemical Synthesis and Reactions
- Catalytic C–H Functionalization Methods
- International Law and Human Rights
- Layered Double Hydroxides Synthesis and Applications
- Organometallic Complex Synthesis and Catalysis
- Crime, Illicit Activities, and Governance
- Iron oxide chemistry and applications
- Heme Oxygenase-1 and Carbon Monoxide
- Fluorine in Organic Chemistry
- Terrorism, Counterterrorism, and Political Violence
- Oxidative Organic Chemistry Reactions
Humboldt-Universität zu Berlin
2020-2024
In soluble methane monooxygenase enzymes (sMMO), dioxygen (O2) is activated at a diiron(II) center to form an oxodiiron(IV) intermediate Q that performs the challenging oxidation of methanol. An analogous mechanism O2 activation mono- or dinuclear iron centers rare in synthetic chemistry. Herein, we report mononuclear non-heme iron(II)-cyclam complex, 1-trans, activates corresponding iron(IV)-oxo 2-trans, via reminiscent process sMMO. The conversion 1-trans 2-trans proceeds formation...
Emulating the capabilities of soluble methane monooxygenase (sMMO) enzymes, which effortlessly activate oxygen at diiron(II) centers to form a reactive diiron(IV) intermediate Q, then performs challenging oxidation methanol, poses significant challenge. Very recently, one us reported mononuclear complex [(cyclam)FeII(CH3CN)2]2+ (1), performed rare bimolecular activation molecule O2 generate two molecules FeIV═O without requirement external proton or electron sources, similar sMMO. In present...
We present a one-pot deprotection/polymerisation protocol for the synthesis of crystalline graphdiynes on top copper surface starting with stable trimethylsilylated alkyne monomers.
Cytochrome c oxidase (CcO) is a heme−copper (HCO) that catalyzes the natural reduction of oxygen to water. A pro-found understanding some elementary steps leading intricate 4e−/4H+ O2 presently lacking. St = 1 FeIII−(O22−)−CuII (IP) intermediate proposed reduce overpotentials associated with reductive O−O bond rupture by allowing electron transfer from tyrosine moiety without necessity any spin-surface crossing. Direct evidence in-volvement IP in HCO catalytic cycle is, however, missing....
Cytochrome c oxidase (CcO) is a heme copper (HCO) that catalyzes the natural reduction of oxygen to water. A profound understanding some elementary steps leading intricate 4e–/4H+ O2 presently lacking. total spin St = 1 FeIII–(O22–)–CuII (IP) intermediate proposed reduce overpotentials associated with reductive O–O bond rupture by allowing electron transfer from tyrosine moiety without necessity any spin-surface crossing. Direct evidence involvement IP in CcO catalytic cycle is, however,...
Abstract Complexes [L 2 Fe][Li(DME)] , 1(DME) {[L Fe][Na (DME) 3 ]} ∞ 2(DME) and Fe][K(DME) ] 3(DME) were synthesized by deprotonation of LH (LH =O(SiPh OH) ) with the respective alkali metal tert ‐butoxides followed recrystallization from DME. It turned out that upon crossing over Li + via Na to K counterions structures high‐spin iron(II) complexes are increasingly distorted a square planar towards tetrahedral structure so represents borderline case, as indicated τ ‐values. The distortions...
The diiron(II) complex, [(OCO)Fe(MeCN)]
We report hitherto elusive side‐on η2‐bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexa‐fluorobenzene) complexes present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine tetrahydrofuran reveals that experimental ligand binding strengths follow order THF < C6H6 C6F6 cyclohexene benzaldehyde anthraquinone. To understand this surprising order, complexes’ electronic structures were...
We report hitherto elusive side‐on η2‐bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexa‐fluorobenzene) complexes present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine tetrahydrofuran reveals that experimental ligand binding strengths follow order THF < C6H6 C6F6 cyclohexene benzaldehyde anthraquinone. To understand this surprising order, complexes’ electronic structures were...
Diiron cofactors in enzymes perform diverse challenging transformations. The structures of high valent intermediates (Q methane monooxygenase and X ribonucleotide reductase) are debated since Fe-Fe distances 2.5-3.4 Å were attributed to "open" or "closed" cores with bridging terminal oxido groups. We report the crystallographic spectroscopic characterization a FeIII2 (μ-O)2 complex (2) tetrahedral (4C) centres short distance (2.52 Å), persisting organic solutions. 2 shows large Fe K-pre-edge...
Abstract Deprotonation of O( i Pr 2 SiOH) ( LH ) with LiO t Bu followed by reaction FeCl in THF led to the complex [ L Fe][Li(THF) ] , which represents a structural and spectroscopic model α‐Fe sites Fe/ZSM‐5. Reaction O solution proceeds rather fast is complete within 200 ms; an intermediate adduct could not be identified stopped‐flow methods. Cooling blue solutions −80 °C growth crystals ⋅THF, analysis XRD revealed FeO 4 core that somewhat distorted from planarity towards tetrahedral...