Aromaticity aromatic hydrocarbon ions

H. Fischer, J. N. Murrell, Theor. Chim. Acta (Berlin) 1, 463 (1963). The Interpretation of the Stability of Aromatic Hydrocarbon Ions by Valence Bond Theory. 

It should be noted that several aromatic hydrocarbon ions with an unpaired electron and threefold or higher axis of symmetry, such as CgHg and CgHg are known to have orbitally degenerate ground states. Linear radicals with orbital moments, such as NO, OH, SH, NCO,... 

In contrast, reversed-phase sorbents have non-polar functional groups, e.g. octadecyl, octyl and methyl, and conversely are more likely to retain non-polar compounds, e.g. polycyclic aromatic hydrocarbons. Ion-exchange sorbents have either cationic or anionic functional groups and when in the ionized form attract compounds of the opposite charge. A cation-exchange phase, such as benzene-sulfonic acid, will extract analytes with positive charges (e.g. phenoxyacid herbicides) and vice versa. A summary of the commercially available silica-bonded sorbents is given in Table 8.1. 

A recent review by Calcote (9) discusses many of the proposed mechanisms of soot nucleation, both neutral and ionic, and presents the case for an ion/molecule scheme, beginning with CoH and sequentially adding primarily acetylene and polyacetylene molecules in rapid condensation and condensation-elimination reactions which lead to polycyclic aromatic hydrocarbon ions of m/z 500 - 1000 amu. This particular ion/molecule soot nucleation model has been elucidated further in an article by Calcote and... 

Similar comments apply to the formation of cyclic, polycyclic and spherical aromatic hydrocarbon ions and molecules, but here the lack of experimental data Is even more severe. 

Nitrous acid or nitrite salts may be used to catalyze the nitration of easily nitratable aromatic hydrocarbons, eg, phenol or phenoHc ethers. It has been suggested that a nitrosonium ion (NO + ) attacks the aromatic, resulting initially in the formation of a nitro so aromatic compound (13). Oxidation of the nitro so aromatic then occurs ... 

Principal component analysis has been used in combination with spectroscopy in other types of multicomponent analyses. For example, compatible and incompatible blends of polyphenzlene oxides and polystyrene were distinguished using Fourier-transform-infrared spectra (59). Raman spectra of sulfuric acid/water mixtures were used in conjunction with principal component analysis to identify different ions, compositions, and hydrates (60). The identity and number of species present in binary and tertiary mixtures of polycycHc aromatic hydrocarbons were deterrnined using fluorescence spectra (61). 

With substances that give up an electron more readily than aromatic hydrocarbons, such as potassium, nickel carbonyl, cyanide ion, or iodide ion, complete transfer of an electron occurs and the TCNE anion radical is formed (11). Potassium iodide is a particulady usefiil reagent for this purpose, and merely dissolving potassium iodide in an acetonitrile solution of TCNE causes the potassium salt of the anion radical to precipitate as bronze-colored crystals. 

Reduction of fullerenes to fullerides — Reversible electrochemical reduction of Ceo in anhydrous dimethylformamide/toluene mixtures at low temperatures leads to the air-sensitive coloured anions Qo" , ( = 1-6). The successive mid-point reduction potentials, 1/2, at -60°C are -0.82, -1.26, -1.82, -2.33, —2.89 and —3.34 V, respectively. Liquid NH3 solutions can also be used. " Ceo is thus a very strong oxidizing agent, its first reduction potential being at least 1 V more positive than those of polycyclic aromatic hydrocarbons. C70 can also be reversibly reduced and various ions up to... 

The reaction with HNO3 is quantitative, and the presence of large concentrations of the nitronium ion, NOi ", in solutions of HNO3, MNO3 and N2O5 in H2SO4 enable a detailed interpretation to be given of the nitration of aromatic hydrocarbons by these solutions. 

An alternative way of eliminating water in the RPLC eluent is to introduce an SPE trapping column after the LC column (88, 99). After a post-column addition of water (to prevent breakthrough of the less retained compounds), the fraction that elutes from the RPLC column is trapped on to a short-column which is usually packed with polymeric sorbent. This system can use mobile phases containing salts, buffers or ion-pair reagents which can not be introduced directly into the GC unit. This system has been successfully applied, for example, to the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples (99). 

Recently, Weissman and his colleagues52 showed that the product is paramagnetic indicating that it results from an electron transfer process giving one unpaired electron to the hydrocarbon ion. Furthermore, they demonstrated30 that electron transfer reactions easily proceed in systems containing aromatic" ions and neutral aromatic hydrocarbon molecules, e.g., naphthalene" + phenathrene - naphthalene -j- phenanthrene". 

Unsubstituted polynuclear aromatic hydrocarbons show intense molecular ions. The aklylated polynuclear aromatics and the alkylated benzenes fragment similarly ... 

In fused ring systems, the positions are not equivalent and there is usually a preferred orientation even in the unsubstituted hydrocarbon. The preferred positions may often by predicted as for benzene rings. Thus it is possible to draw more canonical forms for the arenium ion when naphthalene is attacked at the a position than when it is attacked at the p position, and the a position is the preferred site of attack,though, as previously mentioned (p. 682), the isomer formed by substitution at the p position is thermodynamically more stable and is the product if the reaction is reversible and equilibrium is reached. Because of the more extensive delocalization of charges in the corresponding arenium ions, naphthalene is more reactive than benzene and substitution is faster at both positions. Similarly, anthracene, phenanthrene, and other fused polycyclic aromatic hydrocarbons are also substituted faster than benzene. 

Three significant hydrocarbon ions, [S" ], [9 ] and [10 ], should be mentioned as additional examples of the formation of stable salts of the hydrocarbon ions. The triphenylmethylium ion [8" ], as a prototypical aromatic carbocation, reacts with the chloride ion to give the chloride, a... 

Membranes offer a format for interaction of an analyte with a stationary phase alternative to the familiar column. For certain kinds of separations, particularly preparative separations involving strong adsorption, the membrane format is extremely useful. A 5 x 4 mm hollow-fiber membrane layered with the protein bovine serum albumin was used for the chiral separation of the amino acid tryptophan, with a separation factor of up to 6.6.62 Diethey-laminoethyl-derivatized membrane disks were used for high-speed ion exchange separations of oligonucleotides.63 Sulfonated membranes were used for peptide separations, and reversed-phase separations of peptides, steroids, and aromatic hydrocarbons were accomplished on C18-derivatized membranes. 

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