Oxonium systems

The mode of extraction in these oxonium systems may be illustrated by considering the ether extraction of iron(III) from strong hydrochloric acid solution. In the aqueous phase chloride ions replace the water molecules coordinated to the Fe3+ ion, yielding the tetrahedral FeCl ion. It is recognised that the hydrated hydronium ion, H30 + (H20)3 or HgO,, normally pairs with the complex halo-anions, but in the presence of the organic solvent, solvent molecules enter the aqueous phase and compete with water for positions in the solvation shell of the proton. On this basis the primary species extracted into the ether (R20) phase is considered to be [H30(R20)3, FeCl ] although aggregation of this species may occur in solvents of low dielectric constant. 

Ion-association complexes may be classified into three types non-chelated complexes chelated complexes oxonium systems. 

D. Schinzer, Electrophilic Cyclizations to Heterocycles Oxonium Systems, in Organic Synthesis Highlights //(H. Waldmann, Ed.), VCH, Weinheim, New York, etc., 1995, 173-179. 

The efficiency of the extraction depends on the coordinating ability of the solvent, and on the acidity of the aqueous solution which determines the concentration of the metal complex. Coordinating ability follows the sequence ketones > esters > alcohols > ethers. Many metals can be extracted as fluoride, chloride, bromide, iodide or thiocyanate complexes. Table 4.5 shows how the extraction of some metals as their chloro complexes into diethyl ether varies with acid concentration. By controlling acidity and oxidation-state and choosing the appropriate solvent, useful separations can be achieved. As, for example, the number of readily formed fluoride complexes is small compared. with those involving chloride, it is evident that a measure of selectivity is introduced by proper choice of the complexing ion. The order of selectivity is F > Br > I" > Cl" > SCN". Examples of oxonium systems are included in tabic 4.4. 

The Nernst distribution law applies to metal complexes, but their distribution ratios are determined by several interrelated equilibria. As in the case of organic acids and bases, the efficiency of extraction of metal chelates is pH dependent, and for some ion-association complexes, notably oxonium systems (hydrogen ions solvated with ethers, esters or ketones), inorganic complex ions can be extracted from concentrated solutions of mineral acids. 

The protonated azirine system has also been utilized for the synthesis of heterocyclic compounds (67JA44S6). Thus, treatment of (199) with anhydrous perchloric acid and acetone or acetonitrile gave the oxazolinium perchlorate (207) and the imidazolinium perchlorate (209), respectively. The mechanism of these reactions involves 1,3-bond cleavage of the protonated azirine and reaction with the carbonyl group (or nitrile) to produce a resonance-stabilized carbonium-oxonium ion (or carbonium-nitrilium ion), followed by attack of the nitrogen unshared pair jf electrons to complete the cyclization. 

Entry 4 shows that reaction of a secondary 2-octyl system with the moderately good nucleophile acetate ion occurs wifii complete inversion. The results cited in entry 5 serve to illustrate the importance of solvation of ion-pair intermediates in reactions of secondary substrates. The data show fiiat partial racemization occurs in aqueous dioxane but that an added nucleophile (azide ion) results in complete inversion, both in the product resulting from reaction with azide ion and in the alcohol resulting from reaction with water. The alcohol of retained configuration is attributed to an intermediate oxonium ion resulting from reaction of the ion pair with the dioxane solvent. This would react until water to give product of retained configuratioiL When azide ion is present, dioxane does not efiTectively conqiete for tiie ion-p intermediate, and all of the alcohol arises from tiie inversion mechanism. ... 

The hydroxylation reaction, whose stereochemical course is controlled by the strong inherent preference for the formation of a cis-fused 5,5 ring system, creates a molecule which would appear to be well suited for an intramolecular etherification reaction to give ring E of ginkgolide B (1). Indeed, when a solution of 11 in methylene chloride is exposed to camphorsulfonic acid (CSA), a smooth cycli-zation reaction takes place to give intermediate 10 in an overall yield of 75% from 12. The action of CSA on 11 produces a transient oxonium ion at C-12 which is intercepted intramolecularly by the proximal hydroxyl group at C 4. 

Trimethylsilyl iodide (TMSI) cleaves methyl ethers in a period of a few hours at room temperature.89 Benzyl and f-butyl systems are cleaved very rapidly, whereas secondary systems require longer times. The reaction presumably proceeds via an initially formed silyl oxonium ion. 

This would render an overall process of Sn2 addition in an inverted fashion. In addition, from the model, it appeared that if such an anchimeric assistance indeed existed, Sn2 addition could proceed faster, whereas the SN2 addition pathway could be slowed or even suppressed because the ct c o (of the oxonium bond) is not aligned with the system of the C5a-C5 exo-cyclic olefin in the conformation assumed by 90 (see model). The following experiment would actually support this assertion. 

The use of oxonium and other non-chelated systems can be advantageous where relatively high concentrations of metals are to be extracted as solubility in the organic phase is not likely to be a limiting factor. Metal chelates, on the other hand, have a more limited solubility and are more suited to trace-level work. 

Chojnowski and co-workers have studied the polymerization of octamethyltetrasila-l,4-dioxane, a monomer more basic than cyclosiloxanes, which is capable of forming more stable oxonium ions, and thus being a useful model to study the role of silyloxonium ions.150-152 In recent work, these authors used Olah s initiating system and observed the formation of oxonium ion and its transformation to the corresponding tertiary silyloxonium ion at the chain ends.153 The 29Si NMR spectroscopic data and theoretical calculations were consistent with the postulated mechanism. Stannett and co-workers studied an unconventional process of radiation-initiated polymerization of cyclic siloxanes and proposed a mechanism involving the intermediate formation of silicenium ions solvated by the siloxane... 

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