Cation stabilization

Preformed Carbocationic Intermediates. Propargyl cations stabilized by hexacarbonyl dicobalt have been used to effect Friedel-Crafts alkylation of electron-rich aromatics, such as anisole, /V, /V- dim ethyl a n il in e and 1,2,4,-trimethoxybenzene (24). Intramolecular reactions have been found to be regio and stereo-selective, and have been used ia the preparatioa of derivatives of 9JT- uoreaes and dibenzofurans (25). 

Other, removable cation-stabilizing auxiliaries have been investigated for polyene cyclizations. For example, a sdyl-assisted carbocation cyclization has been used in an efficient total synthesis of lanosterol. The key step, treatment of (257) with methyl aluminum chloride in methylene chloride at —78° C, followed by acylation and chromatographic separation, affords (258) in 55% yield (two steps). When this cyclization was attempted on similar compounds that did not contain the C7P-silicon substituent, no tetracycHc products were observed. Steroid (258) is converted to lanosterol (77) in three additional chemical steps (225). 

Asphalt emulsions are dispersioas of asphalt ia water that are stabilized iato micelles with either an anionic or cationic surfactant. To manufacture an emulsion, hot asphalt is mixed with water and surfactant ia a coUoid mill that produces very small particles of asphalt oa the order of 3 p.m. These small particles of asphalt are preveated from agglomerating iato larger particles by a coatiag of water that is held ia place by the surfactant. If the asphalt particles agglomerate, they could settle out of the emulsion. The decision on whether a cationic or anionic surfactant is used depends on the appHcation. Cationic stabilized emulsions are broken, ie, have the asphalt settle out, by contact with metal or siHcate materials as weU as by evaporation of the water. Siace most rocks are siHcate-based materials, cationic emulsions are commonly used for subbase stabilization and other similar appHcations. In contrast, anionic emulsions only set or break by water evaporation thus an anionic emulsion would be used to make a cold patch compound. 

HCl addition usually proceeds through a carbocation intermediate, with the dominant product resulting from the most stable cation. Compare energies for the possible cations that can be obtained from isoprene (isoprene+H+). Rank them from most to least stable. Examine the geometries of the cations, and sketch one or more Lewis stmctures for each which are consistent with its geometry. Be sure to point out any unusual features. What factors might be responsible for the ordering of cation stability ... 

The presence of the foreign cation stabilizes the crystal structure of a - Mn02 compounds. This manganese dioxide modification (more exactly it is not a real MnOz modification, since the structure contains a considerable proportion of foreign atoms) can be heated to relatively high temperatures (300 - 400 °C) without destruction of the lattice. Although Thackeray et al. reported the synthesis of cation-and water- free a - MnOz [49, 50J, which is reported to be stable up to 300 °C without destruction of the [2 x 2] tunnel structure, it is commonly believed that a small,... 

Carbamates are expected to be more reactive than amides, as the carbamate nitrogen lone pair is more available for cation stabilization than the amide nitrogen lone pair. Cyclization of 1 indeed occurred in the expected manner to give 2 in almost quantitative yield11. 

The solubility of numerous ionic surfactants in water is strongly reduced in the presence of divalent cations. Stability in hard water is thus an important fact for surfactants used as detergents. Their stability can be measured as the amount of divalent cations at which the formation of a poorly soluble surfactant salt leads to permanent turbidity. The values given in the literature can only be... 

According to part 4.1.4 of this article, an increase in cation stability leads to an increase in cationic polymerizability. The latter order agrees satisfactorily with the well-known fact that vinyl ethers (which have an oxygen atom in the neighboring position... 

The results presented in this part show that the characterization of cationic stability by means of a well-adapted reaction energy for the chemical system is better than ordering the cations according to their heats of formation. The importance of considering solvent effects in quantum chemical calculations is indicated by the fact that gas phase results are thereby modified and correspond with the experiments after that. 

Theoretical Consideration of Cation Stabilities and Electronic Structures... 

The facile thermal isomerization (17) of norbornadiene derivatives [71]-[77] to cycloheptatrienes in polar solvents has been explained in terms of the initial heterolytic cleavage of the strained C(l)-C(7) bond (Hoffmann and Hauser, 1965 Lemal et al., 1966 Hoffmann, 1971, 1985 Lustgarten and Richey, 1974 Hoffmann et al., 1986 Bleasdale and Jones, 1993). The resulting zwitterion intermediates are stabilized by the cation-stabilizing groups attached to C(7) and the cyclohexadienyl-type delocalization of the negative charge. 

Knowing that the energy cost of removing core electrons is always excessive, we can predict that the ionization process will stop when all valence electrons have been removed. Thus, a knowledge of ground-state configurations is all that we need to make qualitative predictions about cation stability. 

The lattice energies of these solids are large enough to make the overall reaction energy-releasing despite the large positive second electron affinity of the anions. In addition, three-dimensional arrays of surrounding cations stabilize the - 2 anions in these solids. 

Kuczynski and Thorns also studied the formation of MV in CdS solution using a cationic surfactant, cetyltrimethylammonium bromide, as a stabiliasr. In the presence of ethylenediaminetetraacetate (EOTA), the MV " yield was greatly increased. EDTA and MV " form a complex with a resultant negative charge, which is electrostatically bound to the cationic CdS surface. The MV " formed is repelled by the positive charge of the cationic stabilizer, a fact which makes the charge separation efficient. 

Allylic silanes show a pronounced tendency to react at the a-carbon in the presence of bidentate ligands.148 This regiochemistry is attributed to the preferential stabilization of cationic character by the silyl substituent. The bidentate ligands enhance the electrophilic character of the TS, and the cation stabilization of the silyl group becomes the controlling factor. 

As would be expected for a highly electrophilic species, rhodium-catalyzed carbenoid additions are accelerated by aryl substituents, as well as by other cation-stabilizing groups on the alkene reactant.205 When applied to 1,1-diarylethenes, ERG substituents favor the position trans to the ester group.206 This can be understood in terms of maximizing the interaction between this ring and the reacting double bond. 

Poverenov, E. Leitus, G. Milstein, D. Synthesis and reactivity of the methylene arenium form of a benzyl cation, stabilized by complexation. J. Am. Chem. Soc. 2006, 128, 16450-16451. 

Konovalova, T. A., J. Krzystek et al. (1999). 95-670GHz EPR studies of canthaxanthin radical cation stabilized on a silica-alumina surface. J. Phys. Chem. B 103 5782-5786. 

Considering the above-mentioned facts, according to which simple diazoketones yield dihydrofurans with ketene acetals but cyclopropanes with enol ethers, one exports an interlink between these clear-cut alternatives to exist, i.e. substrates from which both cyclopropanes and dihydrofurans result. In fact, providing an enol ether with a cation-stabilizing substituent in the a-position creates such a situation The Rh2(OAc)4-catalyzed decomposition of -diazoacetophenone in the presence of ethyl vinyl ether produces mainly cyclopropane 82 (R=H), but a small amount of dihydro-... 

Allenyl cations 1 are a stabilized form of vinyl cations1-3 in which the /1-carbon atom of the vinylic structure is part of the substituent which effects the stabilization of the ion via its electron-donating ability. This leads to a resonance hybrid having formally the alkynyl cation structure 2. Allenyl cations should be distinguished from the allenyl substituted carbenium ions 3 formulated as the mesomeric structures of the vinyl cations 4 (dienyl cations) stabilized by an w-vinyl group (equation 1). 

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