Carbon monoxide in ionic liquid

Hardacre C, Holbrey J D, Katdare S P, et al. Alternating copolymerisation of styrene and carbon monoxide in ionic liquids. Green Chem. 

Hardacre, C., Holbrey, J.D., Katdare, S.P. Seddon, K.R. (2002). Alternating Copolymerisation of Styrene and Carbon Monoxide in Ionic Liquids, Green Chem., 4, pp. 143-146... 

D.5.2. Carbon Monoxide. The solubility of CO in ionic liquids is crucial for car-bonylation reactions. However, quantitative measurements are not yet available. In... 

Ohlin, C. A., Dyson, R J., and Laurenczy, G., Carbon monoxide solubility in ionic liquids Determination, prediction and relevance to hydroformylation, Chem. Commun., 1070, 2004. 

Hanc-Scherer FA, Sanchez-Sanchez CM, Ilea P, Herrero E (2013) Surface-sensitive electrooxidation of carbon monoxide in room temperature ionic liquids. ACS Catal 3 2935-2938... 

Electrons in liquid nitrogen, liquid oxygen, and liquid carbon monoxide exhibit ionic mobilities of the order of 10" cm V S" which are thermally activated (Loveland et al., 1972). In liquid nitrogen, an increase of the electron mobility with field strength was observed above 60 kV/cm (Sakai et al., 1983). Gee et al. (1985) proposed the existence of transient negative ions, while Sakai et al. (1993) assume localization of the electron in a bubble. 

In this chapter, the recent advances in amidocarbonylations, cyclohydrocarbonylations, aminocarbonylations, cascade carbonylative cyclizations, carbonylative ring-expansion reactions, thiocarbonylations, and related reactions are reviewed and the scope and mechanisms of these reactions are discussed. It is clear that these carbonylation reactions play important roles in synthetic organic chemistry as well as organometallic chemistry. Some of the reactions have already been used in industrial processes and many others have high potential to become commercial processes in the future. The use of microwave irradiation and substitutes of carbon monoxide has made carbonylation processes suitable for combinatorial chemistry and laboratory syntheses without using carbon monoxide gas. The use of non-conventional reaction media such as SCCO2 and ionic liquids makes product separation and catalyst recovery/reuse easier. Thus, these processes can be operated in an environmentally friendly manner. Judging from the innovative developments in various carbonylations in the last decade, it is easy to anticipate that newer and creative advances will be made in the next decade in carbonylation reactions and processes. 

A combination of 98% H3P04 and 2% water provides a liquid that can be heated to > 200 °C at atmospheric pressures. A high temperature of 150 °C is required to polymerize phosphoric acid to pyrophosporic acid (H4P207), which has a considerably higher ionic conductivity than the parent acid. It was necessary to raise the operating temperature of the fuel cell to 200 °C in order to tolerate a carbon monoxide level of... 

All ionic compounds (for example, NaCl, KCl, and NaN03) are solids at room temperature covalent compounds may be solids (sugar), liquids (H2O, ethanol), or gases (carbon monoxide, carbon dioxide). The three-dimensional crystal structure that is characteristic of ionic compounds holds them in a rigid, solid arrangement, whereas molecules of covalent compounds may be fixed, as in a solid, or more mobile, a characteristic of liquids and gases. 

Wasserscheid et al. found that aluminum chloride dissolves in triflimide ionic liquids to form biphasic solutions. These solutions can be used to promote the Friedel-Crafts acylation reaction, and an interesting variant is the carbonylation of toluene with carbon monoxide (Scheme 5.2-28) [72]. The ionic liquid can be recycled, but the aluminum chloride is lost when the reaction is worked up. 

An alternative description of a molecular solvent in contact with a solute of arbitrary shape is provided by the 3D generalization of the RfSM theory (3D-RISM) which yields the 3D correlation functions of interaction sites of solvent molecules near the solute. It was first proposed in a general form by Chandler, McCoy, and Singer [22] and recently developed by several authors for various systems by Cortis, Rossky, and Friesner [23] for a one-component dipolar molecular liquid, by Beglov and Roux [24, 25] for water and a number of organic molecules in water, and by Hirata and co-workers for water [26, 27], metal-water [26, 28] and metal oxide-water [31] interfaces, orientationally dependent potentials of mean force between molecular ions in a polar molecular solvent [29], ion pairs in aqueous electrolyte [30], and hydration of hydrophobic and hydrophilic solutes alkanes [32], polar molecule of carbon monoxide [33], simple ions [34], protein [35], amino acids and polypeptides [36, 37]. It should be noted that accurate calculation of the solvation thermodynamics for ionic and polar solutes in a polar molecular liquid requires special corrections to the 3D-RISM equations to eliminate the electrostatic artifacts of the supercell treatment employed in the 3D-RISM approach [30, 34]. 

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