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The localized-to-delocalized transition in mixed-valence chemistry.

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox catalysis, has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox catalysis has combined the unparalleled capacity of transition metal catalysis for bond formation with the broad utility of photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation has allowed the engagement of simple starting materials in metal-mediated bond-forming processes. Moreover, electron or energy transfer directly with key organometallic intermediates has provided novel activation modes entirely complementary to traditional catalytic platforms. This Review details and contextualizes the advancements in molecule construction brought forth by metallaphotocatalysis.

Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis.

Electronic communication in heterobinuclear organometallic complexes through unsaturated hydrocarbon bridges

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration of aliphatic C-H bonds. In this manifold, a photocatalyst (PCHAT) exploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds. Selective C-H bond elaboration may be achieved by a judicious choice of the hydrogen abstractor (key parameters are the electronic character and the molecular structure), as well as reaction additives. Different are the classes of PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, a metal-oxo porphyrin and a tris(amino)cyclopropenium radical dication. The processes (mainly C-C bond formation) are in most cases carried out under mild conditions with the help of visible light. The aim of this review is to offer a comprehensive survey of the synthetic applications of photocatalyzed d-HAT.

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C-H Bonds Elaboration

The fields of C-H functionalization and photoredox catalysis have garnered enormous interest and utility in the past several decades. Many different scientific disciplines have relied on C-H functionalization and photoredox strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, and fine chemical synthesis. In this Review, we highlight the use of photoredox catalysis in C-H functionalization reactions. We separate the review into inorganic/organometallic photoredox catalysts and organic-based photoredox catalytic systems. Further subdivision by reaction class-either sp2 or sp3 C-H functionalization-lends perspective and tactical strategies for use of these methods in synthetic applications.

Photoredox-Catalyzed C-H Functionalization Reactions.

An automated adiabatic calorimeter for the temperature range 13 K to 530 K The heat capacities of benzoic acid from 15 K to 305 K and of synthetic sapphire from 60 K to 505 K

Lattice-engineered micromodulation of intramolecular electron-transfer rates in trinuclear mixed-valence iron acetate complexes

Cobalt-Catalyzed Intermolecular Markovnikov Hydroamination of Nonactivated Olefins: N2-Selective Alkylation of Benzotriazole.

Coupling Reaction between Aldehydes and Non-Activated Hydrocarbons via the Reductive Radical-Polar Crossover Pathway.

The heat capacity of the mixed-valence complex [Fe 3 O(O 2 CCH 3 ) 6 (py) 3 ](CHCl 3 ), where py is pyridine, has been measured with an adiabatic calorimeter between 14 and 300 K. A phase transition with two peaks closely centered at 207.14 and 208.19 K has been found

Yuki Kaneko

Papers

An automated adiabatic calorimeter for the temperature range 13 K to 530 K The heat capacities of benzoic acid from 15 K to 305 K and of synthetic sapphire from 60 K to 505 K

Lattice-engineered micromodulation of intramolecular electron-transfer rates in trinuclear mixed-valence iron acetate complexes

Cobalt-Catalyzed Intermolecular Markovnikov Hydroamination of Nonactivated Olefins: N2-Selective Alkylation of Benzotriazole.

Coupling Reaction between Aldehydes and Non-Activated Hydrocarbons via the Reductive Radical-Polar Crossover Pathway.

Heat capacity and phase transition of the mixed-valence compound, hexakis(acetato)oxotris(pyridine)triiron chloroform solvate