Carbon dioxide electron-transfer reduction

Carbon Dioxide (C02). Figures 11.12 and 11.13 illustrate the electron-transfer reduction of C02 in Me2SO at gold, platinum, and mercury electrodes.18,19 Whereas the reduction at a gold electrode is a one-electron per C02 process on a voltammetric time scale, at mercury it is a sequential two-electron process. In both cases the overall reduction is two electrons per C02. The products for anhydrous conditions are C03 and CO, and with H20 present H0C(0)0-and HC(0)0 ... 

The ready reversibility of this reaction is essential to the role that qumones play in cellular respiration the process by which an organism uses molecular oxygen to convert Its food to carbon dioxide water and energy Electrons are not transferred directly from the substrate molecule to oxygen but instead are transferred by way of an electron trans port chain involving a succession of oxidation-reduction reactions A key component of this electron transport chain is the substance known as ubiquinone or coenzyme Q... 

Electron-transfer reactions occur all around us. Objects made of iron become coated with mst when they are exposed to moist air. Animals obtain energy from the reaction of carbohydrates with oxygen to form carbon dioxide and water. Turning on a flashlight generates a current of electricity from a chemical reaction in the batteries. In an aluminum refinery, huge quantities of electricity drive the conversion of aluminum oxide into aluminum metal. These different chemical processes share one common feature Each is an oxidation-reduction reaction, commonly called a redox reaction, in which electrons are transferred from one chemical species to another. 

Dietz and Peover examined the electrochemical reduction of cis and trans stilbene (114) in DMF containing carbon dioxide, 9>. The first electron transfer to trans-114 affords a planar radical anion (115) which then undergoes rapid reaction with carbon dioxide to produce, ultimately, 2,3-diphenylsuc-cinic acid (116) in... 

More complicated reactions that combine competition between first- and second-order reactions with ECE-DISP processes are treated in detail in Section 6.2.8. The results of these theoretical treatments are used to analyze the mechanism of carbon dioxide reduction (Section 2.5.4) and the question of Fl-atom transfer vs. electron + proton transfer (Section 2.5.5). A treatment very similar to the latter case has also been used to treat the preparative-scale results in electrochemically triggered SrnI substitution reactions (Section 2.5.6). From this large range of treated reaction schemes and experimental illustrations, one may address with little adaptation any type of reaction scheme that associates electrode electron transfers and homogeneous reactions. 

The amide functionality plays an important role in the physical and chemical properties of proteins and peptides, especially in their ability to be involved in the photoinduced electron transfer process. Polyamides and proteins are known to take part in the biological electron transport mechanism for oxidation-reduction and photosynthesis processes. Therefore studies of the photochemistry of proteins or peptides are very important. Irradiation (at 254 nm) of the simplest dipeptide, glycylglycine, in aqueous solution affords carbon dioxide, ammonia and acetamide in relatively high yields and quantum yield (0.44)202 (equation 147). The reaction mechanism is thought to involve an electron transfer process. The isolation of intermediates such as IV-hydroxymethylacetamide and 7V-glycylglycyl-methyl acetamide confirmed the electron-transfer initiated free radical processes203 (equation 148). 

The carbon dioxide anion-radical was used for one-electron reductions of nitrobenzene diazo-nium cations, nitrobenzene itself, quinones, aliphatic nitro compounds, acetaldehyde, acetone and other carbonyl compounds, maleimide, riboflavin, and certain dyes (Morkovnik and Okhlobystin 1979). The double bonds in maleate and fumarate are reduced by CO2. The reduced products, on being protonated, give rise to succinate (Schutz and Meyerstein 2006). The carbon dioxide anion-radical reduces organic complexes of Co and Ru into appropriate complexes of the metals(II) (Morkovnik and Okhlobystin 1979). In particular, after the electron transfer from this anion radical to the pentammino-p-nitrobenzoato-cobalt(III) complex, the Co(III) complex with thep-nitrophenyl anion-radical fragment is initially formed. The intermediate complex transforms into the final Co(II) complex with the p-nitrobenzoate ligand. 

The catalytic cycles for reduction of alkyl and atyl halides using Ni(o), Co(i) or Pd(o) species are interrupted by added carbon dioxide and reaction between the first formed carbon-metal bond and carbon dioxide yields an alkyl or aryl car-boxylate. These catalyses reactions have the advantage of occuriiig at lower cathode potentials than the direct processes summarised in Table 4.14. Mechanisms for the Ni(o) [240] and Pd(o) [241] catalysed processes have been established. Carbon dioxide inserts into the carbon-metal bond in an intermediate. Once the carboxy-late-metal species is formed, a further electron transfer step liberates the carboxy-late ion reforming the metallic complex catalyst. 

The oxygen formed clearly comes from H20 and not from C02, because photosynthesis in the presence of water labeled with lgO produces oxygen labeled with 180, whereas carbon dioxide labeled with 180 does not give oxygen labeled with 180. Notice that the oxidation of the water produces two electrons, and that the formation of NADPH from NADP requires two electrons. These reactions occur at different locations within the chloroplasts and in the process of transferring electrons from the water oxidation site to the NADP reduction site, adenosine diphosphate (ADP) is converted to adenosine triphosphate (ATP see Section 15-5F for discussion of the importance of such phosphorylations). Thus electron transport between the two photoprocesses is coupled to phosphorylation. This process is called photophosphorylation (Figure 20-7). 

These are involved in a wide range of electron-transfer processes and in certain oxidation-reduction enzymes, whose function is central to such important processes as the nitrogen cycle, photosynthesis, electron transfer in mitochondria and carbon dioxide fixation. The iron-sulfur proteins display a wide range of redox potentials, from +350 mV in photosynthetic bacteria to —600 mV in chloroplasts. 

Triorganyl-sulfonium, -selenonium and -telluronium salts are reduced by carbon dioxide radical anions/solvated electrons produced in aqueous solution by radiolysis. The radical expulsion accompanying reduction occurred with the expected leaving group propensities, i.e. benzyl > secondary alkyl > primary alkyl > methyl > phenyl. Much higher product yields in the reduction of selenonium and telluronium compounds have been accounted for in terms of a chain reaction with carbon-centred radicals, with formate serving as the chain transfer agent.282... 

From the point of view of organic synthesis, the overall process consists of the formation of carbohydrates (CH20) by the reduction of carbon dioxide. The essence of the process is the use of photochemical energy to split water and concomitantly to reduce C02. Many proteins and small molecules are involved in photosynthetic machinery. Inorganic species are in the centre of photosynthesis as pigments in light harvesting, substrates, products, catalysts, and electron transfer mediators. 

Figure 21.1 Photosensitized electron transfer cycle for the reduction of carbon dioxide in aqueous photosystem consisting of [Ru(bpy)3]2+/R2+/TEOA/Ru- or Os-colloid. TEOA, triethanolamine. (Adapted from Maidan and Willner [94] and Willner et al. [95])...

It was found, that also Ru and Os colloids can act as catalysts for the photoreduction of carbon dioxide to methane [94, 95]. [Ru(bpy)3]2+ plays a role of a photosensitizer, triethanolamine (TEOA) works as an electron donor, while bipyridinium electron relays (R2+) mediate the electron transfer process. The production of hydrogen, methane, and small amounts of ethylene may be observed in such a system (Figure 21.1). Excited [Ru(bpy)3]2+ is oxidized by bipyridinium salts, whereas formed [Ru(bpy)3]3+ is reduced back to [Ru(bpy)3]2+ by TEOA. The reduced bipyridinium salt R + reduces hydrogen and C02 in the presence of metal colloids. Recombination of surface-bound H atoms competes with a multi-electron C02 reduction. More selective reduction of C02 to CH4, ethylene, and ethane was obtained using ruthenium(II)-trisbipyrazine, [Ru(bpz)3]2+/TEOA/Ru colloid system. The elimination of hydrogen evolution is thought to be caused by a kinetic barrier towards H2 evolution in the presence of [Ru(bpz)3]2+ and noble metal catalysts [96]. 

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