Carbon Dioxide and Organometallics

Table of Contents

1. Frontmatter

2. The Carbon Dioxide Molecule and the Effects of Its Interaction with Electrophiles and Nucleophiles

   Michele Aresta, Antonella Angelini

   Abstract

   This chapter discusses the CO₂ molecule in its ground and excited states, correlating the energy to the molecular geometry. The effect of adding or taking out an electron is illustrated, opening the way to the coordination of CO₂ to metal centers. Several modes of bonding of CO₂ are presented and the IR and multinuclear NMR spectroscopic data of transition metal complexes or adducts with Lewis acids and bases are commented. The reactivity of the coordinated heterocumulene is presented through several examples. The use of IR and NMR techniques for determining the molecular behavior of transition metal complexes in solution is exemplified.

3. Metal Complexes Catalyzed Cyclization with CO2

   Jeroen Rintjema, Leticia Peña Carrodeguas, Victor Laserna, Sergio Sopeña, Arjan W. Kleij

   Abstract

   This chapter describes in general terms the catalytic methodology that has been made available for the use of carbon dioxide (CO₂) in cyclization reactions that incorporate an intact CO₂ fragment without changing the formal oxidation state of the carbon center. The major focus of this chapter will be on the most successful organometallic/inorganic complexes that have been used as catalyst systems throughout the last decade and the preferred ligand frameworks leading to elevated reactivity and/or selectivity behavior in CO₂ coupling reactions. Attention will be especially given to homogeneous catalyst systems as they have proven to be more versatile in CO₂ conversion catalysis and often have modular characteristics that allow for optimization of structure–activity relationships. The most important reactions that have been studied in the current context are designated CO₂ “addition” reactions to small molecule heterocycles such as epoxides and aziridines, though more recently other coupling partners such as diamines, dialcohols, and amino nitriles have further advanced the use of CO₂ in organic synthesis providing access to a wider range of structures. This chapter will serve to demonstrate the utility of CO₂ as a carbon reagent in the catalytic formation of the most prominent organic structures using cyclization strategies specifically.

4. Silver-Catalyzed Carboxylation Reaction Using Carbon Dioxide as Carboxylative Reagent

   Wen-Zhen Zhang

   Abstract

   The transformation of carbon dioxide into value-added fine chemicals via homogeneous catalysis has gained much attention since carbon dioxide is an abundant, nontoxic, and inexpensive C1 feedstock. Silver catalysis has emerged as important synthetic methods for a wide range of organic transformations in the last two decades. In silver-catalyzed carboxylation reactions using carbon dioxide as a carboxylative reagent, silver(I) salts or complexes generally serve as a π-Lewis acid catalyst to activate unsaturated systems, especially alkynes, or in situ generate silver acetylides or arylsilver intermediates as reactive carbon nucleophiles. In this chapter, silver-catalyzed cyclization reactions of propargylic alcohols or amines, o-alkynylanilines, and alkynyl ketones with carbon dioxide are reviewed. Also, silver-catalyzed carboxylation of terminal alkynes and arylboronic esters with carbon dioxide is documented.

5. Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

   Charles Romain, Arnaud Thevenon, Prabhjot K. Saini, Charlotte K. Williams

   Abstract

   This review describes selected metal catalysts for the copolymerisation of epoxides and carbon dioxide to produce polycarbonates. It highlights kinetic and mechanistic studies which have implicated di- or (multi-) metallic pathways for this catalysis and the subsequent development of highly active and selective di-/(multi-) nuclear catalysts. The emphasis is on homogeneous di-/bimetallic catalysts.

6. Transition Metal-Free Incorporation of CO2

   Shuai Zhang, Ran Ma, Liang-Nian He

   Abstract

   Carbon dioxide can be regarded as an ideal C₁ chemical feedstock in both academic and pharmaceutical laboratories owing to its abundance, low cost, non-toxicity, and nonflammability. However, due to CO₂ inherent thermodynamic stability and kinetic inertness, it is difficult to convert CO₂ to value-added chemicals under mild conditions. In order to overcome such barriers, numerous useful synthetic methodologies by strategically using highly active catalysts have been developed for the incorporation of CO₂ to organic compounds. Transition metal-free compounds are proved to be promising efficacious catalysts able to activate CO₂ molecule for efficient transformation of CO₂ on the basis of mechanistic understanding at the molecular level. This chapter features recent advances at methodologies for catalytic transformation of CO₂ promoted by organocatalysts (e.g., N-heterocyclic carbenes, frustrated Lewis pairs and superbases), ionic liquids, and main group metal to produce value-added chemicals such as linear or cyclic carbonates, quinazoline-2,4(1H,3H)-diones, alkylidene cyclic carbonates, amino acids, and so on.

7. CO2-Mediated Formation of Chiral Fine Chemicals

   Xiao-Bing Lu

   Abstract

   The utilization of carbon dioxide as a feedstock for the synthesis of organic chemicals can contribute to a more sustainable chemical industry, since CO₂ is an abundant, inexpensive, and nontoxic renewable C₁ resource. Nevertheless, far less attention was paid to the stereochemically controlled catalytic CO₂ fixation/conversion processes. This review therefore aims to principally showcase the recent progress regarding CO₂-mediated formation of chiral fine chemicals, including enantioselective synthesis of cyclic carbonates by asymmetric ring opening of epoxides with CO₂, enantioselective synthesis of oxazolidinones by the coupling reaction of aziridines with CO₂- or base-mediated formation of oxazolidinone from ethanolamines, metal-catalyzed enantioselective synthesis of functional carboxylic acids and derivatives, and enantioselective synthesis of CO₂-based polycarbonates from epoxides.

8. Ni-Catalyzed Synthesis of Acrylic Acid Derivatives from CO2 and Ethylene

   Sebastian Kraus, Bernhard Rieger

   Abstract

   The story of nickelalactones finally ends well. Over three decades after their discovery, catalytic processes have been successfully established to synthesize acrylate derivatives from ethylene and abundantly available carbon dioxide. The performed research during this time in the CO₂ utilization via C–C bond formation with olefins is presented within this review. It gives detailed insights starting from the initial milestones in the 1980s up to modern strategies through cleavage auxiliaries. Different approaches are examined from an experimental and theoretical point of view as the choice of cleavage agent and the corresponding ligand is crucial for the reaction control and suppression of undesired pathways. Methylation of the lactone species led to a first successful liberation of methyl acrylate in stoichiometric amounts. These results led to a vast progress in research with auxiliaries afterward. Upon addition of Lewis acids or strong sodium bases, finally the first two different catalytic routes have been established which are discussed in detail.

9. Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

   Marcel Brill, Faïma Lazreg, Catherine S. J. Cazin, Steven P. Nolan

   Abstract

   The development of sustainable chemical processes is a long-standing challenge. Carbon dioxide represents a renewable C1 building block for organic synthesis and industrial applications as an alternative to other common feedstocks which are based on natural gas, petroleum oil, or coal. Apart from the advantages associated with the nontoxicity and abundance of CO₂, its utilization further enables the reduction in its atmospheric content, which contributes significantly to the greenhouse effect. Although widespread application of CO₂ in organic synthesis – even on an industrial scale – will not be able to fully compensate for the steadily increasing atmospheric quantities produced (mainly by the combustion of fuels), ecological and economical factors make its usage highly desirable. Therefore, tremendous efforts toward activation and utilization of CO₂ have been made by the scientific community over the last 30 years, and, as a result, the number of highly efficient transition metal-catalyzed CO₂-incorporative reactions has increased dramatically, especially within the last decade. The achievements in the development of sustainable and economic chemical processes for the carboxylation of organic molecules with CO₂ are presented in detail in this chapter.

10. Recent Progress in Carbon Dioxide Reduction Using Homogeneous Catalysts

    Lipeng Wu, Qiang Liu, Ralf Jackstell, Matthias Beller

    Abstract

    Efficient chemical transformations of carbon dioxide into value-added chemicals are of growing importance in academic and industrial laboratories. In this respect, the reduction of carbon dioxide to formic acid, methanol etc., offers interesting possibilities. Herein, we describe the recent developments in carbon dioxide reductions mainly focusing on the use of defined organometallic catalysts and in some cases organocatalysts are also included.

11. Backmatter