Tetraalkylammonium trifluoromethanesulfonates as supporting electrolytes

Rousseau, Kathleen; Farrington, G. C.; Dolphin, David

doi:10.1021/jo00797a054

Cited by 31 publications

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“…The second quasireversible wave is attributed to the formation of a ruthenium(II1)-T-cation radical, [RU"'(OEP) "(P"Buj),]? ' (13). The cyclic voltammogram of 9 in CH,Cl, with TBAiCIO,-as suppoiting electrolyte was identical to that of 3 (due to rapid reduction of 9 to 3 in the vicinity of the working electrode at the beginning of the sweep at 0.0 V) ~lnder the same conditions.…”

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confidence: 68%

“…Electrochemical oxidation of acetonitrile solutions of [Ru"'(OEP)(P"Bu,)~'ClO,- (9) at + 1.2 V gave a magentacoloured solution of [Ru"'(OEP)"(P"Buj),]~'2C10,- (13) which was easily converted back to 9, electrochemically or by reducing agents including methanol. Solutions of 13 at 77 K showed a broad esr signal at g,,, = 2.35 (half peak width 80 G) attributable to low spin rutheniurn(II1) (30), and a sharp s;,,,~ = 2.008 cation radical-like signal (peak-to-peak width 10 G).…”

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confidence: 99%

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Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

Barley¹,

Becker²,

Domazetis³

et al. 1983

Can. J. Chem.

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. Can. J. Chem. 61, 2389Chem. 61, (1983.The syntheses and characterization of some ncw octaethylporphyrin complexes of ruthenium(l1) and ruthcnium(lll) are described; the complexes are Ru(OEP)(P"BU~)~. Ru(OEP)(CO)L (L = PPh3, PUBu3), [Ru(OEP)(P"BU,)~]B~, and Ru(0EP)-(PnBu3)Br, where OEP is the dianion of octaethylporphyrin. The Ru(OEP)(CO)EtOH complex, 1, which reversibly loscs the ethanol ligand in CHzC12 solution, undergoes a one-equivalent oxidation at the porphyrin ligand to gencratc the cation-radical [Ru(OEP)"(CO)]+; a purple species of 'Azu ground statc, produced electrochemically in perchlorate mcdia, can coordinate bromide to generate a green 'A,, ground state species that also results from oxidation of 1 using bromine. Coordination of pyridine to [Ru(OEP)'+CO]+ yields the Ru(OEP)"(CO)py species that can also be formcd by electrochemical oxidation of Ru(OEP)(CO)py. Addition of tertiary phosphines (PR3) to the cation-radical carbonyl spccics can lead to formation of [RU(OEP)(PR,)~]+, via an internal electron transfcr proccss from Ru(11) to the OEP" that appears to bc triggered by loss of the CO ligand. A reversible one-electron electrochemical oxidation of RU(OEP)(P"BU,)~ at 0.03 V (vs. Ag/AgCI) in CH2CIz also gives the ruthenium(Il1) biphosphine cation, while a furthcr onc-elcctron oxidation at 1.2 V generates [Ru(OEP)'+(P"BU,)~]'+, a ruthenium(lI1) n-cation radical characterized by esr. Thc [Ru(OEP)(P"Bu,),]Br complcx decomposes in the solid state to a mixture of Ru(OEP)(PUBu,)Br, formed together with free phosphine via an intramolecular ligand exchange, and RU(OEP)(P"BU~)~, formed by rcduction of the initial ionic ruthenium (lI1) [Traduit par le journal]

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confidence: 68%

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confidence: 99%

Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

Barley¹,

Becker²,

Domazetis³

et al. 1983

Can. J. Chem.

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“…14, 15 Hydrogen tetrafluoroborate (HBF 4 ) was added to a saturated aqueous solution of an equimolar tetra-n-butylammonium bromide. 14, 15 Hydrogen tetrafluoroborate (HBF 4 ) was added to a saturated aqueous solution of an equimolar tetra-n-butylammonium bromide.…”

Section: Methodsmentioning

confidence: 99%

Solvent Effects on the Resonance Raman and Electronic Absorption Spectra of Bacteriochlorophyll a Cation Radical

et al. 1996

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Resonance Raman and electronic absorption spectra of bacteriochlorophyll a cation radical (BChl a •+ ) were recorded in 14 different kinds of solvents. The frequency of the ring-breathing Raman band of BChl a •+ was in the region of 1596-1599 cm -1 in solvents forming the pentacoordinated state in neutral bacteriochlorophyll a (BChl a), while it was in the region of 1584-1588 cm -1 in solvents forming the hexacoordinated state. BChl a •+ exhibited a key absorption band in the regions 546-554 and 557-563 nm in the above penta-and hexacoordinating solvents. Therefore, it has been concluded that the penta-and hexacoordinated states are retained even after conversion of BChl a into BChl a •+ (one-electron oxidation). Application of this rule to the case of 2-propanol solution showed transformation from the penta-to the hexacoordinated state upon one-electron oxidation in this particular solution. The coordination states of BChl a •+ could be correlated with the donor number (DN) and the Taft parameters, and π*, of the solvent: The hexacoordinated state was formed in solvents with DN g 18 or > 0.5 showing higher electron-donating power, while the pentacoordinated state was formed in solvents with π* > 0.65 showing higher dielectric stabilization. Preferential solvation of a hexacoordinating solvent over a pentacoordinating solvent in their mixture (methanol/ acetone or tetrahydrofuran/methylene chloride) was seen in both BChl a and BChl a •+ , but the constant of preferential solvation was increased approximately 3 times by one-electron oxidation.

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“…They were unable to obtain pure quaternary ammonium carboxylates, which would be the ideal supporting electrolytes. Dolphin, et al pointed out that anodic oxidation reactions between tetrafluoroborate and electrochemically generated cations and cation radicals may interfere with the electrochemical reaction under investigation and suggested tetraalkylammonium trifluoromethanesulfonate as an alternative (45).…”

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confidence: 99%

Quarternary ammonia salts: Some recent applications in organic synthesis

Varughese¹

1977

J. Chem. Educ.

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Some recent applications in organic synthesisMost undergraduate organic textbooks give only a passing reference to the unique class of compounds called quaternary ammonium salts. They are often referred to merely as the final products of exhaustive alkylation of primary amines. A student may get the erroneous impression that they are of no particular use in chemistry and that, being ionic, they are all soluble in water. Many textbooks make unqualified statements about their thermal stability.In the last ten years there has been a great upsurge of interest in the chemistry of quaternary ammonium salts. As a result, a number of interesting applications of molten quaternary ammonium salts have resulted (1-5). More recently, Starks reported that a small amount of quaternary ammonium salt added to certain two-phase organic reaction mixtures would catalyze these reactions to a remarkable extent (6). This phenomenon of phase-transfer catalysis has spurred considerable study in the United States, Europe, and Japan as evidenced by the large number of papers published in this area during the past four years.Part of the attractiveness of this area of research stems from the fact that it is within the scope and reach of most institutions where undergraduate research in chemistry is encouraged. No expensive and sophisticated instruments are required, and most of the chemicals needed are relatively inexpensive. Quaternary Ammonium SaltsQuaternary ammonium salts are compounds of the general formula R4N+X_ where R is alkyl, aryl, or aralkyl group and X is any anion. The R groups could be identical or different.These organic salts are ionic compounds which are made from primary, secondary or tertiary amines and an appropriate alkyl halide, sulfate, or some other similar compound carrying an excellent leaving group. Synthesis from a primary amine involves treatment with an excess of alkyl halide in methanol, acetonitrile, ethyl acetate, or benzene solution in the presence of a mild base. The last alkylation step is recognized as the Menshutkin reactionMany of these salts are crystalline solids at room temperature and are stable at their melting points for short periods of time. Low-melting salts may not crystallize easily at room temperature and a few salts are liquids at laboratory temperature (6-9). Their melting points depend on molecular weight, symmetry of the cation, and the nature of the anion. Thermal stability is related to the nucleophilicity of the anion. Strongly nucleophilic anions promote reverse Menschutkin reaction. Elimination products will also be obtained if the tertiary amine formed in the reverse Menschutkin reaction is not promptly removed from the reaction mixture. Hygroscopic properties vary in poorly defined fashion.Low-molecular weight salts up to Cg-salts are highly soluble in water, but beyond that the solubility in water decreases rapidly. However, incorporation of ether linkages in one or more of the alkyl groups tends to increase the solubility in water remarkably. Quaternary ammonium salts are gener...

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Tetraalkylammonium trifluoromethanesulfonates as supporting electrolytes

Cited by 31 publications

References 0 publications

Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

Solvent Effects on the Resonance Raman and Electronic Absorption Spectra of Bacteriochlorophyll a Cation Radical

Quarternary ammonia salts: Some recent applications in organic synthesis

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