4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Transformation of carbon dioxide.

Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2.

The increase in atmospheric carbon dioxide is linked to climate changes; hence there is an urgent need to reduce the accumulation of CO2 in the atmosphere. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 buildup. This review covers six important CO2 transformations namely: chemical transformations, photochemical reductions, chemical and electrochemical reductions, biological conversions, reforming and inorganic transformations. Furthermore, the vast research area of carbon capture and storage is reviewed briefly. This review is intended as an introduction to CO2, its synthetic reactions and their possible role in future CO2 mitigation schemes that has to match the scale of man-made CO2 in the atmosphere, which rapidly approaches 1 teraton.

The teraton challenge. A review of fixation and transformation of carbon dioxide

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing

State of the art and perspectives in catalytic processes for CO2 conversion into chemicals and fuels: The distinctive contribution of chemical catalysis and biotechnology

Role of the macrocyclic polyether in the synthesis of N-alkylcarbamate esters from primary amines, CO2 and alkyl halides in the presence of crown-ethers.

This book provides an analysis of the reaction mechanisms relevant to a number of processes in which CO2 is converted into valuable products. Several different processes are considered that convert CO2 either in specialty chemicals or in bulk products or fuels. For each reaction, the mechanism is discussed and the assessed steps besides the dark sites of the reaction pathway are highlighted. From the insertion of CO2 into E-X bonds to the reduction of CO2 to CO or other C1 molecules or else to C2 or Cn molecules, the reactions are analysed in order to highlight the known and obscure reaction steps. Besides well known reaction mechanisms and energy profiles, several lesser known situations are discussed. Advancing knowledge of the latter would help to develop efficient routes for the conversion of CO2 into valuable products useful either in the chemical or in the energy industry. The content of this book is quite different from other books reporting the use of CO2. On account of its clear presentation, Reaction Mechanisms in Carbon Dioxide Conversion targets in particular researchers, teachers and PhD students

Reaction Mechanisms in Carbon Dioxide Conversion

One of the many goals of the green chemistry movement is to eliminate the use of phosgene (COCl{sub 2}), an extremely hazardous compound used in many syntheses, including the production of carbamates, organic carbonates, and polymers. One of the most interesting options for eliminating this compound is to replace it with CO{sub 2}. In addition to carbon dioxide`s abundance and benign nature, it has the benefits of recycling carbon and of reducing the amount of CO{sub 2} released into the atmosphere when its use is linked with other processes that emit CO{sub 2}. Several synthetic strategies that do not use phosgene are under development. The authors briefly review the most interesting ones and then expand on the use of CO{sub 2} as a potential building block for organic carbamates, carbonates, and isocyanates. One of these routes, polycarbonate synthesis, is already in industrial-scale operation: PAC Polymers Inc. currently produces CO{sub 2}-epoxide copolymers. The synthesis of carbamates and substituted ureas has been developed, and this process awaits industrial exploitation.

Eugenio Quaranta

Papers

State of the art and perspectives in catalytic processes for CO2 conversion into chemicals and fuels: The distinctive contribution of chemical catalysis and biotechnology

Role of the macrocyclic polyether in the synthesis of N-alkylcarbamate esters from primary amines, CO2 and alkyl halides in the presence of crown-ethers.

Reaction Mechanisms in Carbon Dioxide Conversion

Carbon dioxide: A substitute for phosgene

Mechanistic studies on the role of carbon dioxide in the synthesis of methylcarbamates from amines and dimethylcarbonate in the Presence of CO2.