Tetrabutylammonium hexafluorophosphate

TETRABUTYLAMMONIUM HEXAFLUOROPHOSPHATE ANDBIS(4,4, 5,5 -TETRAMETHYL-2,2-BI-l,3-DISELENOLY-LIDENE) RADICAL ION (1 + ) HEXAFLUOROPHOSPHATE 

Submitted by DENNIS A. STEPHENS and JACK M. WILLIAMSt Checked by MARSHA M. LEEt 

Recrystallization from aqueous ethanol, or from absolute ethanol, followed by drying in vacuum at 70 °C for 10 h. 

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In 1985, Sullivan et al. reported a voltammetric study on (Bipy)Re[CO]3Cl in acetonitrile with tetrabutylammonium hexafluorophosphate (TBAHFP) as the supporting electrolyte. 

Figure 6.20 Cyclic voltammograms of the first (a) at 8000 V/s and second (b) at 140 V/s generation of dendrimers containing a hexaphenylbenzene core and 6 and 12 C60 units, respectively (THF in the presence of 0.3 M of tetrabutylammonium hexafluorophosphate as supporting electrolyte).74 Reproduced with permission from Ref. 74.

Figure 3.55 Cyclic voltammograms or Re(Bipy)(CO)3CI in CHjCN/O.l M tetrabutylammonium hexafluorophosphate as supporting electrolyte at a button Pt electrode, and with a sweep rate of 200mV s"(a) The switching potential characteristics of the coupled chemical reactions in the ahsence of C02. The lettered redox processes are discussed in the text, (b) The effect of saturating the solution with C02. From Sullivan et al (19155).

Figure 12.4 Cyclic voltammograms of 1 mM diphenylanthracene in acetonitrile containing 0.01 M tetrabutylammonium hexafluorophosphate. Scan rate 115 V/s. Solid line voltammogram recorded at a disk electrode with a 14 /xm radius. Dashed line voltammogram recorded at a disk electrode with a 0.91 mm radius.

Figure 12.5 Cyclic voltammograms for the reduction of 1 mM cobaltocenium (Cp2Co+) hexafluorophosphate and oxidation of 1 mM ferrocene (Cp2Fe) in acetonitrile recorded at a band electrode (width = 4.6 / m) at a scan rate of 10 mV s 1. The supporting electrolyte is tetrabutylammonium hexafluorophosphate at (A) 0.02 M, (B) 0.2 mM, (C) 2.0 mM, and (D) 20 mM. [From Ref. 68, reprinted with permission of the copyright holder.]...

This solvent is fairly pure as received. The only impurities are water and traces of dimethyl sulfide. Dimethyl sulfide can be removed by a preliminary vacuum distillation, or by bubbling an inert gas through the solution for 10 to 20 min before use. The water content can be reduced to 10 ppm by sequential treatment with two batches of 3 A molecular sieves (activation of the sieve at 500°C for 16 h in an inert atmosphere has been advocated [62], but activation for 15 h at 300°C should suffice [52]). Calcium hydride and a number of other basic reagents have been advocated as drying agents, but in fact all of these are ineffective [32]. Tetrabutylammonium hexafluorophosphate exhibits good solubility in THF. 

MeNP, 2-methyl-2-nitropropane NPent, 1-nitropentane NPh, 3-nitrophenol COT, cycloocta-tetraene TPE, tetraphenylethylene TBAP, tetrabutylammonium perchlorate TEABr, tetraethyl-ammonium bromide TBAPIy, Tetrabutylammonium hexafluorophosphate MeCN, acetonitrile DMSO, dimethylsulfoxide DCM, dichloromethane [42]... 

Room temperature argon-purged dichloromethane solution and reversible and monoelectronic processes, unless otherwise noted tetrabutylammonium hexafluorophosphate as supporting electrolyte, glassy carbon as working electrode. bPurified tetrahydrofurane under vacuum conditions. Irreversible process potential value estimated by the DPV peak. 

Electrochemical fluorination 168,169> is a commercial process for perfluorina-tion of aliphatic compounds. The reaction is performed in liquid hydrogen fluoride -potassium fluoride at a nickel anode. The mechanism is not known free fluorine cannot be detected during electrolysis, so it seems probable that fluorination is a direct electrochemical reaction. Theoretically, hydrogen fluoride-potassium fluoride should be a very oxidation-resistant SSE, and it might well be that the mechanism is analogous to that proposed for anodic acetamidation of aliphatic compounds in acetonitrile-tetrabutylammonium hexafluorophosphate 44 K... 

Fig. 25 Cyclic voltammogram of complex 45 measured in acetonitrile in the presence of 0.1 M tetrabutylammonium hexafluorophosphate as supporting electrolyte with 100 mV s 1 scan rate. The black line shows the scan between - 2.4 to 1 V, and the gray line between - 2.8 to 1 V. The observed irreversible new wave at around - 1.35 V is due to unknown product that is formed when scanning to more negative potential...

Data for solutions in CHjClj/O.1 Af tetrabutylammonium hexafluorophosphate unless noted otherwise. bData in parenthesis for CH3CN solutions. cNot given in reference. 

Diphenyl ditellurium was electrochemically reduced to benzenetellurolate in acetonitrile with sonication in anH-type cell. Tetrabutylammonium hexafluorophosphate served as the electrolyte. The cathode was a cylindrical graphite cloth and the anode a platinum grid. The cathodic solution was purged with argon. The potential had to be changed from — 1.20 to — 2.35 V during the reduction1-3. 

Benzenetellurolate, generated by electrochemical reduction of diphenyl ditellurium in a solution of tetrabutylammonium hexafluorophosphate, reacted with electrochemically partly reduced chlorobenzonitriles5 and bromobenzophenones6 to produce aryl phenyl tellurium compounds in moderate yields. The following compounds were isolated from the reaction mixtures ... 

Figure 7. ECL intensity from 0.38 mM DPA in CH3CN containing 0.1 M tetrabutylammonium hexafluorophosphate at a 1 pm Pt disk (-) and simulations of the profiles, assuming diffusion-limited annihilation of DPA" " and DPA . From Collinson, M. M. et al., J. Phys. Chem., 1994, 98, 11942, with permission from the American Chemical Society.

The electropolymerization of ferrocene/thiophene conjugates [65] was conducted by oxidation on a Pt electrode and led to the deposition of a monolayer of poly (thiophene). The electropolymerization was performed from several solution systems, such as tetrabutylammonium hexafluorophosphate/acetonitrile and lithium perchlorate/acetonitrile, at a concentration of 0.1 M. Constant potential experiments (+ 2.0 V) for a definite time were used to effect polymerization. Polymerization was also attempted using cyclic voltammetry (repeatedly sweeping from 0.0 to + 2.5 V) and pulse potential (potential stepped from 0.0 to 2.0 V and back to 0.0 V). 

DMF = dimethylformamide NMP = A-methylpyrrolidone HMPA = hexamethylphosphotriamide DMSO = dimethyl sulfoxide sulfolane = tetramethylene sulfone PC = propylene carbonate THF = tetrahydrofuran, HFP = hexafluoro-2-propanol TBAP, TBAI = tetrabutylammonium perchlorate or iodide, respectively TEAP, TEAB = tetraethylammomum perchlorate or bromide, respectively TBAPFg = tetrabutylammonium hexafluorophosphate. 

In this Chapter the following common abbreviations are used CV, cyclic voltammetry RDE, rotating disk electrode rds, rate-determining step TBABF4, tetrabutylammonium tetrafluoroborate TBAPF6, tetrabutylammonium hexafluorophosphate TEAP, tetraethylammonium perchlorate TBAP, tetrabutylammonium perchlorate DMSO, dimethyl... 

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