On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

The recently described intermolecular O₂ transfer between the side‐on Ni‐O₂ complex [(12‐TMC)Ni‐O₂]⁺ and the manganese complex [(14‐TMC)Mn]²⁺, where 12‐TMC and 14‐TMC are 12‐ and 14‐membered macrocyclic ligands, 12‐TMC=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane and 14‐TMC=1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long‐range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two‐step reaction, with a first rate‐determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ‐η¹:η¹‐O₂ coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.     

Versatile Iridicycle Catalysts for Highly Efficient and Chemoselective Transfer Hydrogenation of Carbonyl Compounds in Water

Cyclometalated iridium complexes are shown to be highly efficient and chemoselective catalysts for the transfer hydrogenation of a wide range of carbonyl groups with formic acid in water. Examples include α‐substituted ketones (α‐ether, α‐halo, α‐hydroxy, α‐amino, α‐nitrile or α‐ester), α‐keto esters, β‐keto esters and α,β‐unsaturated aldehydes. The reduction was carried out at substrate/catalyst ratios of up to 50 000 at pH 4.5 and required no organic solvent. The protocol provides a practical, easy and efficient way for the synthesis of β‐functionalised secondary alcohols, such as β‐hydroxyethers, β‐hydroxyamines and β‐hydroxyhalo compounds, which are valuable intermediates in pharmaceutical, fine chemical, perfume and agrochemical synthesis.     

High-Pressure Synthesis of Fully Occupied Tetragonal and Cubic Tungsten Bronze Oxides

A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K₃W₅O₁₅ (K_0.6WO₃). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of R_W=3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze K_xWO₃-K_0.6−yBa_yWO₃ phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO₃ phase was also identified as a line phase—in marked contrast to Na_xWO₃ and Li_xWO₃ with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended.     

Enantioselective Synthesis of (+)-Mitomycin K by a Palladium-Catalyzed Oxidative Tandem Cyclization

The mitomycins, a family of bioactive natural products, feature a compact 6/5/5-fused polycyclic ring structure densely decorated with highly reactive and/or fragile quinone, amino ketal, and aziridine as well as carbamate moieties. It is this striking feature that has defeated numerous synthetic attempts towards these apparently small molecules, rendering them one of the most formidable targets for total synthesis. We herein report the first enantioselective synthesis of (+)-mitomycin K, a representative of G series mitomycins. The key step of this synthesis is an enantioselective oxidative cyclization catalyzed by a palladium/(+)-sparteine system that had previously been developed by our group. The robustness of this method bodes well for further applications in the asymmetric total synthesis of natural products, particularly those with characteristic 6/5/5-fused pyrroloindole skeletons.     

The Interstitial Carbon of the Nitrogenase FeMo Cofactor is Far Better Stabilized than Previously Assumed

The first quantum-mechanical calculations of all relevant potential constants in both the iron-molybdenum cofactor and the iron-vanadium cofactor of nitrogenase suggest that the carbide is bound to the center of the enzyme much more strongly than hitherto assumed. Previous studies seemed to indicate a dummy function of the interstitial carbon, with a weak force constant (ca. 0.32 N cm⁻¹). Our new investigations confirm a different picture: the central carbon atom binds the iron-sulfur cluster through six covalent C−Fe bonds. With a potential constant of more than 1.3 N cm⁻¹, the interstitial carbon also appears to be dynamically persistent. According to our investigations, the values for the elasticity within the iron-sulfur cluster have to be corrected too. These new details on the mechano-chemical properties of the FeMo cofactor will be important for elucidating the catalytic cycle of nitrogen fixation. By implementing our new algorithm in the freely available COMPLIANCE program, the dependence on the coordinates during the calculation of Hesse matrices is eliminated completely.     

Activation and Photoinduced Release of Alkynes on a Biomimetic Tungsten Center: The Photochemical Behavior of the W−S-Phoz System

The synthesis and structural determination of four tungsten alkyne complexes coordinated by the bio-inspired S,N-donor ligand 2-(4′,4′-dimethyloxazoline-2′-yl)thiophenolate (S-Phoz) is presented. A previously established protocol that involved the reaction of the respective alkyne with the bis-carbonyl precursor [W(CO)₂(S-Phoz)₂] was used for the complexes [W(CO)(C₂R₂)(S-Phoz)₂] (R=H, 1 a ; Me, 1 b ; Ph, 1 c ). Oxidation with pyridine-N-oxide gave the corresponding W-oxo species [WO(C₂R₂)(S-Phoz)₂] (R=H, 2 a ; Me, 2 b ; Ph, 2 c ). All W-oxo-alkyne complexes ( 2 a , b , c ) were found to be capable of alkyne release upon light irradiation to afford five-coordinate [WO(S-Phoz)₂] ( 3 ). The photoinduced release of the alkyne ligand was studied in detail by in situ ¹H NMR measurements, which revealed correlation of the photodissociation rate constant ( 2 b>2 a>2 c ) with the elongation of the alkyne C≡C bond in the molecular structures. Oxidation of [WO(S-Phoz)₂] ( 3 ) with pyridine-N-oxide yielded [WO₂(S-Phoz)₂] ( 4 ), which shows highly fluxional behavior in solution. Variable-temperature ¹H NMR spectroscopy revealed three isomeric forms with respect to the ligand arrangement versus each other. Furthermore, compound 4 rearranges to tetranuclear oxo compound [W₄O₄(μ-O)₆(S-Phoz)₄] ( 5 ) and dinuclear [{WO(μ-O)(S-Phoz)}₂] ( 6 ) over time. The latter two were identified by single-crystal X-ray diffraction analyses.     

A Chemical Proteomic Analysis of Illudin-Interacting Proteins

The illudin natural product family are fungal secondary metabolites with a characteristic spirocyclopropyl-substituted fused 6,5-bicyclic ring system. They have been extensively studied for their cytotoxicity in various tumor cell types, and semisynthetic derivatives with improved therapeutic characteristics have progressed to clinical trials. Although it is believed that this potent alkylating compound class acts mainly through DNA modification, little is known about its binding to protein sites in a cellular context. To reveal putative protein targets of the illudin family in live cancer cells, we employed a semisynthetic strategy to access a series of illudin-based probes for activity-based protein profiling (ABPP). While the probes largely retained potent cytotoxicity, proteomic profiling studies unraveled multiple protein hits, suggesting that illudins exert their mode of action not from addressing a specific protein target but rather from DNA modification and unselective protein binding.     

Devisable POM/Ni Foam Composite: Precisely Control Synthesis toward Enhanced Hydrogen Evolution Reaction at High pH

Polyoxometalates (POMs) are promising catalysts for the electrochemical hydrogen production from water owing to their high intrinsic catalytic activity and chemical tunability. However, poor electrical conductivity and easy detachment of the POMs from the electrode cause significant challenges under operating condition. Herein, a simple one-step hydrothermal method is reported to synthesize a series of Dexter–Silverton POM/Ni foam composites (denoted as Ni M -POM/Ni; M =Co, Zn, Mn), in which the stable linkage between the POM catalysts and the Ni foam electrodes lead to high activity for the hydrogen evolution reaction (HER). Among them, the highest HER performance can be observed in the NiCo-POM/Ni, featuring an overpotential of 64 mV (at 10 mA cm⁻², vs. reversible hydrogen electrode), and a Tafel slope of 75 mV dec⁻¹ in 1.0 m aqueous KOH. Moreover, the NiCo-POM/Ni catalyst showed a high faradaic efficiency ≈97 % for HER. Post-catalytic of NiCo-POM/Ni analyses showed virtually no mechanical or chemical degradation. The findings propose a facile and inexpensive method to design stable and effective POM-based catalysts for HER in alkaline water electrolysis.     

A Coumarin Triflate Reagent Enables One-Step Synthesis of Photo-Caged Lipid Metabolites for Studying Cell Signaling

Photorelease of caged compounds is among the most powerful experimental approaches for studying cellular functions on fast timescales. However, its full potential has yet to be exploited, as the number of caged small molecules available for cell biological studies has been limited by synthetic challenges. Addressing this problem, a straightforward, one-step procedure for efficiently synthesizing caged compounds was developed. An in situ generated benzylic coumarin triflate reagent was used to specifically functionalize carboxylate and phosphate moieties in the presence of free hydroxy groups, generating various caged lipid metabolites, including a number of GPCR ligands. By combining the photo-caged ligands with the respective receptors, an easily implementable experimental platform for the optical control and analysis of GPCR-mediated signal transduction in living cells was developed. Ultimately, the described synthetic strategy allows rapid generation of photo-caged small molecules and thus greatly facilitates the analysis of their biological roles in live cell microscopy assays.     

Contribution of Discharge Excited Atomic N,N2*, and N2+ to a Plasma/Liquid Interfacial Reaction as Suggested by Quantitative Analysis

Electric-discharge nitrogen comprises three main types of excited nitrogen species-atomic nitrogen (N_atom), excited nitrogen molecules (N₂*), and nitrogen ions (N₂⁺) – which have different lifetimes and reactivities. In particular, the interfacial reaction locus between the discharged nitrogen and the water phase produces nitrogen compounds such as ammonia and nitrate ions (denoted as N-compounds generically); this is referred to as the plasma/liquid interfacial (P/L) reaction. The N_atom amount was analyzed quantitatively to clarify the contribution of N_atom to the P/L reaction. We focused on the quantitative relationship between N_atom and the produced N-compounds, and found that both N₂* and N₂⁺, which are active species other than N_atom, contributed to P/L reaction. The production of N-compounds from N₂* and N₂⁺ was enhanced upon UV irradiation of the water phase, but the production of N-compounds from N_atom did not increase by UV irradiation. These results revealed that the P/L reactions starting from N_atom and those starting from N₂^* and N₂⁺ follow different mechanisms.