A fundamental aim in the field of catalysis is the development of new modes of small molecule activation. One approach toward the catalytic activation of organic molecules that has received much attention recently is visible light photoredox catalysis. In a general sense, this approach relies on the ability of metal complexes and organic dyes to engage in single-electron-transfer (SET) processes with organic substrates upon photoexcitation with visible light.

Many of the most commonly employed visible light photocatalysts are polypyridyl complexes of ruthenium and iridium, and are typified by the complex tris(2,2′-bipyridine) ruthenium(II), or Ru(bpy)32+ (Figure 1). These complexes absorb light in the visible region of the electromagnetic spectrum to give stable, long-lived photoexcited states.1,2 The lifetime of the excited species is sufficiently long (1100 ns for Ru(bpy)32+) that it may engage in bimolecular electron-transfer reactions in competition with deactivation pathways.3 Although these species are poor single-electron oxidants and reductants in the ground state, excitation of an electron affords excited states that are very potent single-electron-transfer reagents. Importantly, the conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes.






Open in a separate window


Figure 1


Ruthenium polypyridyl complexes: versatile visible light photocatalysts.

/pdf/visible-light-photoredox-catalysis-with-transition-metal-5d1oxrsczo.pdf

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

2.1.2. Low Topology/Framework Density 1003 2.1.3. Side Group Directed Superstructures 1003 2.2. Synthesis Considerations 1003 2.3. Special Properties 1004 3. Metal Imidazolate Frameworks 1004 3.1. Chains and Rings 1004 3.2. Zeolitic and Zeolite-like Frameworks 1006 3.2.1. SOD-Type Zinc(II) 2-Methylimidazolate 1007 3.3. Nonporous 4-Connected Networks 1010 3.4. Polyimidazolates 1011 4. Metal Pyrazolate Frameworks 1011 4.1. Clusters and Chains 1011 4.2. 3D Networks Based on Polypyrazolates 1012 5. Metal 1,2,4-Triazolate Frameworks 1014 5.1. Simple 3-Connected Networks 1015 5.2. Quasi-Imidazolates 1018 5.3. With Coordinative Substituents 1019 5.4. With Secondary Counterions and/or Ligands 1021 6. Metal 1,2,3-Triazolate Frameworks 1023 7. Metal Tetrazolate Frameworks 1025 7.1. Univalent Coinage-Metal Tetrazolate Frameworks 1025

Metal Azolate Frameworks: From Crystal Engineering to Functional Materials

Introduction Cationic domino reactions Anionic domino reactions Radical domino reactions Pericyclic domino reactions Photochemically induced domino processes Transition metal catalysis Domino reactions initiated by oxidation or reduction Enzymes in domino reactions Multicomponent reactions Special techniques in domino reactions

Domino Reactions in Organic Synthesis

I. Introduction. Background. Focus of the review. Review procedure and results. The NEA-TDB data base system. Presentation of the selected data. II. Standards and Conventions. Symbols, terminology and nomenclature. Units and conversion factors. Standard and reference conditions. Fundamental physical constants. III. Selected Uranium Data. IV. Selected Auxiliary Data. V. Discussion of Data Selection. Elemental uranium. Aqua ions. Oxide, hydride and hydroxide species. VI. Discussion of Auxiliary Data Selection. Reference list. Authors list. Formula list. Discussion of selected references. Ionic strength corrections. Assigned uncertainties. The estimation of entropies.

Chemical thermodynamics of uranium

A number of oxidative enzymes from bacteria, fungi and plants have been reported to play an important role in numerous waste treatment applications. Peroxidases and/or phenoloxidases can act on specific recalcitrant pollutants by precipitation or transforming to other products and permitting a better final treatment of the waste. Improvement in the useful life and thereby a reduction in treatment cost has been accomplished through enzyme immobilization. Horseradish peroxidase, lignin peroxidase and manganese peroxidase mineralize a variety of recalcitrant aromatic compounds. Immobilization of these enzymes on porous ceramic supports or resins did not adversely affect their stability and showed a good potential for degradation of environment persistent aromatics. Tyrosinase, which catalyzes the hydroxylation of phenols and dehydrogenation of o-diphenols, in an immobilized form exerted an excellent phenol removal. Laccase is capable of eliminating the phenols through polymerization process, however, the presence of mediator such as ABTS and HBT degraded phenol by oxidative process. Many applications with oxidative enzymes and plant materials in effluent as in soil remediation will be discussed.

Potential applications of oxidative enzymes and phenoloxidase-like compounds in wastewater and soil treatment: a review

In the course of our investigations on new boronic acid based carbohydrate sensors three new boronic acids 3, 7 and 11 containing a ferrocene moiety were synthesised. Their design includes an intramolecular B–N bonding motif in order to facilitate binding at physiological pH. We report the synthesis of the compounds and our investigations on glucose complexation as studied by 13C NMR spectroscopy. The crystal structure of 2,4,6-tris[2-(N-ferrocenylmethyl-N-methylaminomethyl)phenyl]boroxin (13) (boroxin of boronic acid 3) (boroxin = cyclotriboroxane) was obtained and compared with structures obtained of 2,4,6-tris[2-(N,N-dimethylaminomethyl)phenyl]boroxin (14) and 2,2-dimethyl-1,3-diyl[2-(N,N-dimethylaminomethyl)phenyl]boronate
(15). The structure of 13 shows the existence of intramolecular B–N bonds in the solid phase.

Design, synthesis and structure of new potential electrochemically active boronic acid-based glucose sensors

/pdf/cyclic-voltammetry-and-electrocatalysis-of-the-blue-copper-28sv4a2mqa.pdf

Cyclic Voltammetry and Electrocatalysis of the Blue Copper Oxidase Polyporus versicolor Laccase.

/pdf/redox-properties-of-free-radicals-158y4n0hvj.pdf

Redox properties of free radicals

/pdf/a-neutron-diffraction-study-of-the-crystal-and-molecular-11gdrvgmik.pdf

A Neutron Diffraction Study of the Crystal and Molecular Structure of Pyrazole, C3H4N2.

/pdf/on-the-crystal-structure-of-a-new-vanadium-oxide-v4-o9-3ukj7ct91w.pdf

Inger Søtofte

Papers

Design, synthesis and structure of new potential electrochemically active boronic acid-based glucose sensors

Cyclic Voltammetry and Electrocatalysis of the Blue Copper Oxidase Polyporus versicolor Laccase.

Redox properties of free radicals

A Neutron Diffraction Study of the Crystal and Molecular Structure of Pyrazole, C3H4N2.

On the crystal structure of a new vanadium oxide, V4 O9