Selective hydroxylation of benzene to phenol Cu(μ-O˙)Cu intermediate using a nonsymmetric dicopper catalyst.

The one-step oxidation of benzene to phenol represents a significant and promising advancement in modern industries focused on the production of high-value-added chemical products. Nevertheless, challenges persist in achieving sufficient catalytic selectivity and preventing over-oxidation. Inspired by copper enzymes, we present a nonsymmetric dicopper complex ([CuII2(TPMAN)(μ-OH)(HO)], 1) for the selective oxidation of benzene to phenol.

Pivotal Role of Geometry Regulation on O-O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts.

In this study, we highlight the impact of catalyst geometry on the formation of O-O bonds in Cu and Fe catalysts. A series of Cu complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, the catalytic performance of these Cu complexes is enhanced as their molecular skeletons become more rigid, which contrasts with the behavior observed in our previous investigation with Fe analogs.

Identifying Metal-Oxo/Peroxo Intermediates in Catalytic Water Oxidation by In Situ Electrochemical Mass Spectrometry.

Molecular catalysis of water oxidation has been intensively investigated, but its mechanism is still not yet fully understood. This study aims at capturing and identifying key short-lived intermediates directly during the water oxidation catalyzed by a cobalt-tetraamido macrocyclic ligand complex using a newly developed an in situ electrochemical mass spectrometry (EC-MS) method. Two key ligand-centered-oxidation intermediates, [(L)CoOH] and [(L)CoOOH], were directly observed for the first time, and further confirmed by O-labeling and collision-induced dissociation studies.

Bioinspired Trinuclear Copper Catalyst for Water Oxidation with a Turnover Frequency up to 20000 s.

Solar-powered water splitting is a dream reaction for constructing an artificial photosynthetic system for producing solar fuels. Natural photosystem II is a prototype template for research on artificial solar energy conversion by oxidizing water into molecular oxygen and supplying four electrons for fuel production. Although a range of synthetic molecular water oxidation catalysts have been developed, the understanding of O-O bond formation in this multielectron and multiproton catalytic process is limited, and thus water oxidation is still a big challenge.

Lanthanide Silylamide-Catalyzed Synthesis of Pyrano[2,3-]indol-2-ones.

A lanthanide silylamide-catalyzed tandem reaction of isatins, diethyl phosphite, and 2,3-diarylcyclopropenones has been developed. A series of pyrano[2,3-]indol-2-ones were synthesized in high yields. The cooperation of the Lewis acidity of the lanthanide center and the Bronsted basicity of the N(SiMe) anion may be the key factor affecting the catalytic activity of lanthanide amides.

Redox-Active Ligand Assisted Catalytic Water Oxidation by a Ru =O Intermediate.

Water splitting is one of the most promising solutions for storing solar energy in a chemical bond. Water oxidation is still the bottleneck step because of its inherent difficulty and the limited understanding of the O-O bond formation mechanism. Molecular catalysts provide a platform for understanding this process in depth and have received wide attention since the first Ru-based catalyst was reported in 1982.

Visible-Light-Enabled Decarboxylative Sulfonylation of Cinnamic Acids with Sulfonylhydrazides under Transition-Metal-Free Conditions.

Decarboxylative cross-coupling reactions of cinnamic acids with sulfonylhydrazides were explored using oxygen as the sole terminal oxidant, realizing a conceptually novel technology for vinyl sulfone synthesis under the synergistic interactions of visible light irradiation, organic dye-type photocatalyst eosin Y, KI, and Cs2CO3 at room temperature.