Dissociation, tetrabutylammonium

With the decrease in permittivity, however, complete dissociation becomes difficult. Some part of the dissolved electrolyte remains undissociated and forms ion-pairs. In low-permittivity solvents, most of the ionic species exist as ion-pairs. Ion-pairs contribute neither ionic strength nor electric conductivity to the solution. Thus, we can detect the formation of ion-pairs by the decrease in molar conductivity, A. In Fig. 2.12, the logarithmic values of ion-association constants (log KA) for tetrabutylammonium picrate (Bu4NPic) and potassium chloride (KC1) are plotted against (1 /er) [38]. 

An alternative suggestion is that the coordinated monomer dissociates to give an oxyanion stabilized by the nucleophile s counterion, most commonly, tetrabutylammonium or cesium ions,69 by analogy to the mechanism proposed for activation of tributylstannyl ethers by nucleophiles.57 This proposal is summarized in Fig. 14, which also shows the product mixture obtained for methyl (2S,3R)-2,3-dihydroxybutanoate. For this compound, reaction on the oxygen atom of the inherently less acidic hydroxyl is favored. Both anions, E and F, are in equilibrium with the coordinated monomer, and the less populated (but more reactive) anion E reacts to a greater extent, or in other words, the difference in the rate constants for trapping is greater than the difference in equilibrium constants. 

Unlike lithium halides, tetrabutylammonium halides are fully dissociated in PDC, but they are associated in HMPA, and this is in agreement with simple electrostatic considerations. Similar results have been found in DMF, where alkali metal halides are fully dissociated whereas tetraaUcylammonium halides are associated 56, 57). 

A detailed study was carried out on (benzophenonylmethyl)-tri- -butylammonium triphenylbutylborate (BTAB). Nano- and picosecond laser photolysis demonstrated electron transfer from the borate counteranion to the excited triplet state of the benzophenone moiety. This leads to formation of a benzophenone moiety and a boranyl radical that dissociates rapidly to form butyl radicals. In the nonpolar solvent benzene the short lifetime of the triplet state (300 ps) suggests an intra-ion-pair process. The addition of 1 % MeCN caused an increase in the triplet lifetime to 1.2 ns, suggesting formation of a solvent-separated ion pair. For a lO" m solution in neat MeCN triplet decay is a function of tetrabutylammonium triphenyl- -butylborate concentration. 

The exciplexes formed between arenes and good acceptors such as dicyanobenzene can dissociate to radical ion pairs if the solvent used is sufficiently polar. The radical cation of the arene is then susceptible to attack by nucleophiles and this can lead to products of addition or substitution of the arene. A preliminary account of how salts such as tetrabutylammonium tetrafluoroborate can serve to mediate the charge separation in less polar solvents was reported last year. A second paper from the same group has now been published which describes the formation of the amino substituted dihydrophenanthrene (86) during the irradiation of a solution of phenanthrene, dicyanobenzene and propylamine in relatively non-polar solvents such as THF in the presence of tetrabutylammonium tetrafluoroborate. In the absence of the salt no product is formed. 

Here, we consider electropolymerized 3,4-ethylenedioxythiophene (EDT), prepared with different supporting electrolytes (see [135]) polystyrenesulfonic add (PSS), p-toluenesulfonic acid (Tos), and tetrabutylammonium perchlorate (BU4NCIO4). The anion produced from the dissociation of toluene-sulfonic acid is also called tosylate (< -SO i). Additionally, we address chemically prepared PEDOT-PSS, in a water emulsion, sodium free (<0.5 ppm), provided by Agfa Gevaert N.V. None of these blends contains PSS -Na" ", as was the case for Baytron P discussed above. The conductivity values a obtained for the polymers are summarized in Table 21.1. PEDOT/Tos is the most conductive (450 S cm ). The polyanion-based materials give lower conductivities 80 S cm for electropolymerized PEDOT-PSS and 0.03 S cm for chemically polymerized PEDOT-PSS. 

Even when using the more polar SCFs, the issue of electrolyte conductivity is very important for electrochemical studies. Conductivity depends on the solubility of the electrolyte, the dissociation of the ions, and the mobility of the ions in the SCR In most of the reported studies, commercially available electrolytes were employed (e.g., tetrabutylammonium tetrafluoroborate) that are conventionally used for nonaqueous electrochemistry. For example, when Olsen and Tallman [67] measured the equivalent conductivity for concentrations of tetrabutylammonium tetrafluoroborate between 6 and 13 mM in SCCHCIF2 at 388 K, and for pressures from 10 to 24 MPa, they found a nonlinear increase in equivalent conductivity with the square-root of electrolyte concentration. Such behavior is indicative... 

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