A series of 2,3-dicarboxylato-5-acetyl-4-aminoselenophenes, 5a – j , was obtained via the uncommon assembly of building blocks on a diiron platform, starting from commercial [Fe 2 Cp 2 (CO) 4 ] through the stepwise formation of diiron complexes [ 2a – d ]CF 3 SO 3 , 3a – d , and 4a – j . The selenophene-substituted bridging alkylidene ligand in 4a – j is removed from coordination upon treatment with water in air under mild conditions (ambient temperature in most cases), affording 5a – j in good to excellent yields. This process is highly selective and is accompanied by the disruption of the organometallic scaffold: cyclopentadiene (CpH) and lepidocrocite (γ-FeO(OH)) were identified by NMR and Raman analyses at the end of one representative reaction. The straightforward cleavage of the linkage between a bridging Fischer alkylidene and two (or more) metal centers, as observed here, is an unprecedented reaction in organometallic chemistry: in the present case, the carbene function is converted to a ketone which is incorporated into the organic product. DFT calculations and electrochemical experiments were carried out to give insight into the release of the selenophene-alkylidene ligand. Compounds 5a – j were fully characterized by elemental analysis, mass spectrometry, IR, and multinuclear NMR spectroscopy and by X-ray diffraction and cyclic voltammetry in one case.

Cationic Ru(ii) arene complexes with α-diimine ligands were investigated as catalytic precursors in the transfer hydrogenation of ethyl levulinate to γ-valerolactone from isopropanol under MW irradiation.

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Diiron bis-cyclopentadienyl bis-carbonyl cationic complexes with a bridging vinyliminium ligand, [Fe2Cp2(CO)(μ-CO){μ-η1:η3-C3(R′)C2HC1NMe(R″)}]CF3SO3 (R = Xyl = 2,6-C6H3Me2, R′ = Ph, R″ = H, 2a; R = Xyl, R′ = R″ = Me, 2b; R = R′ = Me, R″ = H, 2c; R = Me, R′ = 2-naphthyl, R″ = H, 2d; R = Me, R′ = R″ = Ph, 2e), are easily available from commercial chemicals, robust in aqueous media and exert a variable in vitro cytotoxicity against cancer cell lines depending on the nature of the substituents on the vinyliminium ligand. The anticancer activity is, at least in part, associated to fragmentation reactions, leading to iron oxidation and active neutral and well-defined monoiron species. We report an innovative synthetic procedure for the preparation of 2a,c,d, and a facile method to access the monoiron derivative of 2a, i.e., [FeCp(CO){C1(NMeXyl)C2HC3(Ph)C(O)}] (3a). According to IC50 analyses at different times of incubation of the complexes, 3a is significantly faster in inhibiting cell viability compared to its diiron precursor 2a. The neutral complexes [Fe2Cp2(CO)(μ-CO){μ-k1N:k1C:k1C-C3(R′)C2(Se)C1(NMe2)C4(CO2Y)C5(CO2Y)}] (R′ = Y = Me, 4a; R′ = Pr, Y = tBu, 4b; R′ = Y = Et, 4c) are obtained via the two-step modification of the vinyliminium moiety and comprise a bridging selenophene-decorated alkylidene ligand. The antiproliferative activity exhibited by 4a-c is moderate but comparable on the ovarian cancer cell line A2780 and the corresponding cisplatin resistant cell line, A2780cisR. Complexes 4a-c in aqueous solutions undergo progressive release of the alkylidene ligand as a functionalized selenophene, this process being slower in cell culture medium. Since the released selenophenes SeC1{C(O)R′}C2(NMe2)C3(CO2Y)C4(CO2Y) (R′ = Y = Me, 5a; R′ = Pr, Y = tBu, 5b) are substantially not cytotoxic, it is presumable that the activity of 4a-c is largely ascribable to the {Fe2Cp2(CO)2} scaffold.

Photocatalysts which are stable to photocorrosion and noble metal‐free, are highly desirable to achieve a light‐driven hydrogen production which satisfies the criteria of low production cost and environmental sustainability. Herein, a new heterostructure TiO2/BP/CoP has been developed, in which the BP nanosheets interact strongly with TiO2 and CoP, speeding up the transfer of photogenerated electrons and thus increasing H2 production. Once BP is added to TiO2 (P25) as only 1 % wt., the H2 evolution rate increases up to 4 times reaching a value of 830 μmol/g ⋅ h under UV‐Vis light irradiation. By integrating CoP nanoparticles as a cocatalyst up to 2 % wt., H2 production is further promoted to 7400 μmol/g ⋅ h, 37 times higher than pristine TiO2. Photoluminescence and electrochemical impedance measurements show that this heterostructure achieves a much more efficient charge separation and reduction of the internal resistance in comparison to pristine TiO2. Combining these data with UV‐Vis diffuse reflectance and Mott‐Schottky, a plausible mechanism was proposed.