title: Semiconductor Photocatalysis for Chemoselective Radical Coupling Reactions.
abstract: Photocatalysis at semiconductor surfaces is a growing field of general photocatalysis because of its importance for the chemical utilization of solar energy. By analogy with photoelectrochemistry the basic mechanism of semiconductor photocatalysis can be broken down into three steps: photogenerated formation of surface redox centers (electron-hole pairs), interfacial electron transfer from and to substrates (often coupled with proton-transfer), and conversion of primary redox intermediates into the products. Sun driven water cleavage and carbon dioxide fixation are still in the state of basic research whereas aerial degradation reactions of pollutants have reached practical application for the cleaning of air. In addition, a great variety of organic transformations (not syntheses) have been reported. They include cis-trans isomerizations, valence isomerizations, cycloaddition reactions, intramolecular or intermolecular C-N and C-C couplings, partial oxidations, and reductions. In all cases, well-known products were formed but very rarely also isolated. As compared to conventional homogeneous organic synthesis, the photocatalytic reaction mode is of no advantage, although the opposite is quite often claimed in the literature. It is also noted that a high quantum yield does not implicate a high product yield, since it is measured at very low substrate conversion in order to minimize secondary photoreactions. That is especially important in semiconductor photocatalysis since photocorrosion of the photocatalyst often prevents long-time irradiation, as is the case for colloidal metal sulfide semiconductors, which in general are photochemically too unstable to be used in synthesis. In this Account, we first classify the numerous organic photoreactions catalyzed by semiconductor powders. The classification is based on easily obtainable experimental facts, namely the nature of the light absorbing reaction component and the reaction stoichiometry. Next we discuss the problem of quantitative comparisons of photocatalytic activities or apparent quantum yields and propose a basic three-step mechanistic model. Finally, we address the question whether or not the unique photoredox properties of simple inorganic semiconductor powders may lead to previously unknown visible light induced organic syntheses. For that, we summarize novel radical C-C- and C-N- couplings photocatalyzed by self-prepared cadmium sulfide powders. Electron acceptor and donor substrates like imines or 1,2-diazenes, and cyclic olefins or unsaturated ethers, respectively, undergo a linear addition reaction. The hitherto unknown products have all been isolated in good to moderate yields and may be of pharmaceutical interest. In the first reaction step photogenerated electron-hole pairs produce through proton-coupled electron transfer the corresponding radicals. Their subsequent chemoselective heterocoupling affords the products, correlating with an insertion of the imine or 1,2-diazene into an allylic C(sp3)-H bond of the donor substrate. In the absence of an imine or 1,2-diazene, cyclic allyl/enol ethers are dehydrodimerized under concomitant hydrogen evolution. Even a visible light photosulfoxidation of alkanes is catalyzed by titania. In these heterogeneous photoredox reactions the role of the semiconductor photocatalyst is multifunctional. It induces favorable substrate preorientations in the surface-solvent layer, it catalyzes proton-coupled interfacial electron transfer to and from substrates generating intermediate radicals, and it enables their subsequent chemoselective coupling in the surface-solvent interface. Different from molecular photosensitizers, which enable only one one-electron transfer with one single substrate, photoexcited semiconductors induce two concerted one-electron transfer reactions with two substrates. This is because the light generated electron-hole pairs are trapped at distinct surface sites and undergo proton-coupled interfacial electron transfers with unsaturated donor and acceptor substrates. The radicals diffuse in a solid-solute-surface layer to undergo chemo- and stereoselective C-C and C-N bond formation. Thus, the semiconductor photocatalyst functions like an artificial leaf. Since several minerals are known to have semiconductor properties, solar photocatalysis may be also relevant for prebiotic and environmental chemistry.
authors.affiliation: Institute of Inorganic Chemistry, University of Erlangen-Nürnberg , D-91058 Erlangen, Germany.
authors.forename: Horst
authors.identifier: 0000-0003-1042-7967
authors.initials: H
authors.lastname: Kisch