Supercritical fluids organometallic complexes

Although modifiers are added to supercritical fluids to increase their polarity, they can also impart decreased polarity, aromaticity, chirality and the ability to further complex organometallic compounds. Just as carbon dioxide is the most popular substance for use as a supercritical fluid, it is also that to which modifiers are most frequently added. This is so because modifiers are seen as the means for enabling the use of CO, in situations where it may not be the best solvent. For example, methanol is added to supercritical CO, to increase its polarity, aliphatic hydrocarbons to decrease it, toluene to impart aromaticity, [/ ]-2-butanol to add chirality and tributyl phosphate to enhance the solvation of metal complexes. The amount of modifier to be added depends on the properties of the extractant and those of the analyte and matrix usually, it ranges from a few... 

Time-resolved Infrared spectroscopy (TRIR), a combination of UV flash photolysis and fast IR spectroscopy (ns), has been outstandingly successful in identifying reactive intermediates [5] and excited states [6] of metal carbonyl complexes in solution at room temperature. We have used infrared spectroscopy to probe the mechanism of photo-17] and electrochemical [8] catalytic reduction of COj. We have used TRIR to study organometallic reactions in supercritical fluids on a nanosecond time-scale [9-10]. 

Coordination compounds can be dissolved in supercritical fluids such as C02, N20, pentane, and diethylether by incorporating dionate, carbonyl, and fluorinated groups.33 Much less work on novel compound synthesis has been reported although a number of inorganic materials and organometallic complexes have been prepared. For example, the amide [Cr2(NH2)3(NH3)6]I3 was prepared from Crl2 by dissolution in supercritical NH3.34... 

Reactions that otherwise would be carried out in more than one phase (heterogeneous reactions) can be transformed to homogeneous ones, with the aid of supercritical fluids, where interphase transport limitations are eliminated. This is realized due to enhanced solubilities of the supercritical fluids. Typical examples are reactions in water (supercritical water can solubilize organic compounds), homogeneous catalytic reactions, reactions of organometallic compounds. Homogenizing one compound more than the other may also affect relative rates in complex reactions and enhance the selectivity. 

The use of supercritical fluids as reaction media for organometallic species is also investigated. Reactions include photochemical replacement of carbon monoxide with N2 and H2 in metal carbonyls, where the reaction medium is supercritical xenon. Also, photochemical activation of C-H bonds by organometallic complexes in supercritical carbon dioxide is investigated. More recent studies on photochemical reactions also include laser flash photolysis of metal carbonyls in supercritical carbon dioxide and ethane and laser flash photolysis of hydrogen abstraction reaction of triplet benzophenone in supercritical ethane and... 

Erkey and co-workers [59-61] prepared Pt- and Ru-doped carbon aerogels using a supercritical deposition method. This involved dissolution of an organometallic precursor in a supercritical fluid and the exposure of a solid substrate to this solution. After impregnation of the support with the metal precursor, it was converted to the metal form by different methods. Dimethyl(l,5-cyclooctadiene) platinum(ll) was used as a precursor for Pt [59,60], and two different Ru complexes, trisacetylacetonate Ru(lll) and Ru(cod)(tmhd)2, were used for Ru [61], Monolithic organic and carbon aerogels... 

Supercritical fluids (SCFs) have proved to be versatile media for a wide range of chemical processes [1] from stereoselective organic chemistry [2] through catalytic hydrogenation [3], polymer synthesis [4] and polymer modification [5] to the preparation of novel inorganic materials [6] and organometallic complexes [7]. IR and Raman spectroscopy have played a significant role [8] in many of these developments. 

Studying Highly Reactive Organometallic Complexes with Infrared Spectroscopy Matrix Isolation, Liquefied Noble Gases, Supercritical Fluids, and Time-resolved IR Spectroscopy... 

A third approach (Figure 6.14.9c) uses organometaDic catalysts in sohd modifications, for example, covalently bonded (see above) or immobilized in supported liquid form (see below). Here the reaction remains a sohd/supercritical fluid biphasic system during reaction and again the SCCO2 is used as the mobile phase to contact the reactant intimately with the immobilized organometallic complex. 

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