ACS Organic & Inorganic Au最新文献

Monodentate phosphine-ligated nickel compounds, e.g., [Ni(PPh₃)₄] are relevant as active catalysts across a broad range of reactions. This report expands upon the coordination chemistry of this family, offering the reactivity of allyl- and vinyl-substituted diphenylphosphine (PPh₂R) with [Ni(COD)₂] (COD = 1,5-cyclooctadiene). These reactions provide three-coordinate dinickelacycles that are intermolecularly tethered through adjacent {Ni}-olefin interactions. The ring conformation of such cycles has been studied in the solid-state and using theoretical calculations. Here, a difference in reaction outcome is linked to the presence of an allyl vs vinyl group, where the former is observed to undergo rearrangement, bringing about challenges in clean product isolation.

A family of chiral iodoaniline-lactate based catalysts with C₁ and C₂ symmetry were efficiently synthesized. Comparisons between the reactivity and selectivity between the new and previously reported catalysts are made. The new catalysts promoted the α-oxysulfonylation of ketones in shorter reaction times and with higher yields of up to 99%. A scope for the oxysulfonylation reaction is presented, forming a variety of reported and novel products with enantioselectivities of up to 83%.

We present here new synthetic strategies for the isolation of a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands (MIC) of the 1,2,3-triazole-5-ylidene type, in which the bpy ligands (bpy = 2,2′-bipyridine) of the archetypical [Ru(bpy)₃]²⁺ have been successively replaced by one, two, or three pyridyl-MIC ligands. Three new complexes have been isolated and investigated via NMR spectroscopy and single-crystal X-ray diffraction analysis. The incorporation of one MIC unit shifts the potential of the metal-centered oxidation about 160 mV to more cathodic potential in cyclic voltammetry, demonstrating the extraordinary σ-donor ability of the pyridyl-MIC ligand, while the π-acceptor capacities are dominated by the bpy ligand, as indicated by electron paramagnetic resonance spectroelectrochemistry (EPR-SEC). The replacement of all bpy ligands by the pyridyl-MIC ligand results in an anoidic shift of the ligand-centered reduction by 390 mV compared to the well-established [Ru(bpy)₃]²⁺ complex. In addition, UV/vis/NIR-SEC in combination with theoretical calculations provided detailed insights into the electronic structures of the respective redox states, taking into account the total number of pyridyl-MIC ligands incorporated in the Ru(II) complexes. The luminescence quantum yield and lifetimes were determined by time-resolved absorption and emission spectroscopy. An estimation of the excited state redox potentials conclusively showed that the pyridyl-MIC ligand can tune the photoredox activity of the isolated complexes to stronger photoreductants. These observations can provide new strategies for the design of photocatalysts and photosensitizers based on MICs.

Oxychalcogenides are emerging as promising alternative candidates for a variety of applications including for energy. Only few phases among them show the presence of Q–Q bonds (Q = chalcogenide anion) while they drastically alter the electronic structure and allow further structural flexibility. Four original oxy(poly)chalcogenide compounds in the system Ba–V–Q–O (Q = S, Se) were synthesized, characterized, and studied using density functional theory (DFT). The new structure type found for Ba₇V₂O₂S₁₃, which can be written as Ba₇S(VS₃O)₂(S₂)₃, was substituted to yield three selenide derivatives Ba₇V₂O₂S_9.304Se_3.696, Ba₇V₂O₂S_7.15Se_5.85, and Ba₇V₂O₂S_6.85Se_6.15. They represent original multiple-anion lattices and first members in the system Ba–V–Se–S–O. They exhibit in the first layer heteroleptic tetrahedra V⁵⁺S₃O and isolated Q^2– anions and in the second layer dichalcogenide pairs (Q₂)^2– with Q = S or Se. Selenide derivatives were attempted by targeting the selective substitution of isolated Q^2– or (Q₂)^2– (in distinct layers) or both by selenide, but it systematically led to concomitant and partial substitution of both sites. A DFT meta-GGA study showed that selective substitution yields local constraints due to rigid VO₃S and pairs. Experimentally, incorporation of selenide in both layers avoids geometrical mismatch and constraints. In such systems, we show that the interplay between the O/S anionic ratio around V⁵⁺, together with the presence/nature of the dichalcogenides (Q₂)^2– and isolated Q^2–, impacts in unique manners the band gap and provides a rich background to tune the band gap and the symmetry.

The selective oxidation of methane to methanol, using H₂O₂ generated in situ from the elements, has been investigated using a series of ZSM-5-supported AuPd catalysts of varying elemental composition, prepared via a deposition precipitation protocol. The alloying of Pd with Au was found to offer significantly improved efficacy, compared to that observed over monometallic analogues. Complementary studies into catalytic performance toward the direct synthesis and subsequent degradation of H₂O₂, under idealized conditions, indicate that methane oxidation efficacy is not directly related to H₂O₂ production rates, and it is considered that the known ability of Au to promote the release of reactive oxygen species is the underlying cause for the improved performance of the bimetallic catalysts.

We report the isolation and study of dimers stemming from popular thiazol-2-ylidene organocatalysts. The model featuring 2,6-di(isopropyl)phenyl (Dipp) N-substituents was found to be a stronger reducing agent (E_ox = −0.8 V vs SCE) than bis(thiazol-2-ylidenes) previously studied in the literature. In addition, a remarkable potential gap between the first and second oxidation of the dimer also allows for the isolation of the corresponding air-persistent radical cation. The latter is an unexpected efficient promoter of the radical transformation of α-bromoamides into oxindoles.

C₂-Symmetrical scaffolds are privileged ligands in metal catalysis and are also widely used in organocatalysis. Among these, 2,5-disubstituted pyrrolidines hold a paramount importance, especially since they also find application in medicinal chemistry. This review highlights the stereoselective syntheses of these C₂-symmetrical nitrogen heterocycles. It includes synthetic strategies based on the use of the chiral pool as well as the more recent sequences designed following major achievements in asymmetric catalysis.

Regioselective phosphonation of pyridines is an interesting transformation in synthesis and medicinal chemistry. We report herein a metal-free approach enabling access to various 4-phosphonated pyridines. The method consists of simply activating the pyridine ring with a Lewis acid (BF₃·OEt₂) to facilitate the nucleophilic addition of a phosphine oxide anion. The formed sigma complex is subsequently oxidized with an organic oxidant (chloranil) to yield the desired adducts in good to excellent yields. We furthermore showed that access to C2-phosphoinated pyridines can be achieved in certain cases with strong Lewis basic phosphorus nucleophiles or with strong Lewis acidic pyridines. Both experimental and computational mechanistic investigations were undertaken and allowed us to understand the factors controlling the reactivity and selectivity of this reaction.

Amalgams have played an important role in fundamental and applied solid-state chemistry and physics because of the diversity of crystallographic features and properties that they have to offer. Moreover, their peculiar chemical properties can sometimes give rise to unconventional superconducting or magnetic ground states. In the current work, we present an in-depth analysis of single crystals of YHg₃ and LuHg₃ (Mg₃Cd structure type, space group P6₃/mmc). Both compounds show superconductivity below T_c = 1 ± 0.1 K (YHg₃) and T_c = 1.2 ± 0.1 K (LuHg₃). Given the high air-sensitivity and toxicity of these compounds, this study was only possible using a number of dedicated experimental techniques.