Boron photochemistry.  I.  Irradiation of sodium tetraarylborates in aqueous solution

Williams, J. L. R.; Doty, J. C.; Grisdale, Patrick J.; Searle, Roger; Regan, Thomas H.; Happ, G. P.; Maier, D.

doi:10.1021/ja00996a013

Cited by 83 publications

(36 citation statements)

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“…C60 • -is oxidized to C60 with O2 dissolved in the NB solution, 8 . [24][25][26] Indeed, the 1 H NMR spectra proved the existence of biphenyl in the decomposition products. However, since we could synthesize neither [Ph2BO] -nor (dihydroxy)-diphenylborate ([Ph2B(OH)2] -), we could not decide whether these compounds were included in the decomposition products or not.…”

Section: Ion Transfer (It) Of Decomposition Products Of Tpb -Producedmentioning

confidence: 94%

Evidences of Electron Transfer of a Fullerene Anion Radical (C60•-) Prepared under Visible-Light Illumination at a Nitrobenzene/Water Interface

et al. 2016

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Experimental Apparatus and procedureVoltammetric measurements at an NB/W interface were performed with a four-electrode potentiostat (Hokuto, HA1010mM1A) controlled by a personal computer. The electrolytic cell, shown in Fig. 1(a), was machined from poly(chlorotrifluoroethylene) resin blocks, and was placed in a shield case in order to avoid electric noise. 3-or proton, absorption bands of C60 • -in a visible/near infrared absorption spectrum disappeared. This disappearance supports the ET across the NB/W interface. This finding is significant as both an example of ET at a liquid/liquid interface including photochemical reactions and the photochemistry of C60.

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Section: Ion Transfer (It) Of Decomposition Products Of Tpb -Producedmentioning

confidence: 94%

Evidences of Electron Transfer of a Fullerene Anion Radical (C60•-) Prepared under Visible-Light Illumination at a Nitrobenzene/Water Interface

et al. 2016

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“…Inspection of equation 16 shows an unusually large pre-exponential factor and a larger than typical activation energy of 143 kJ/mole versus more common values of 50-100 kJ/mole. Thus equation 16 probably does not correspond to a theoretical expectation for any simple mechanism.…”

Section: Sodium Tetraphenylborate Decompositionmentioning

confidence: 97%

“…The process subsequently blends the resulting waste slurry, containing radioactive cesium and less than 10 percent of the original organic compounds, with high level radioactive sludge and transfers the mixture to a vitrification facility for processing into borosilicate glass for long-term storage. Other studies investigated tetraphenylborate decomposition using chemical oxidation [13][14][15], photolytic [16][17][18], electrochemical [19][20][21] and radiolytic processes [22][23][24][25]. Decomposition products identified in these studies include diphenylborinic acid, phenylboronic acid, biphenyl, benzene and phenol.…”

Section: Phenylborate Decomposition: Hydrolysis and Reactions Involvimentioning

confidence: 99%

“…Several authors report decomposition schemes involving oxidation of tetraphenylborate by chemical [13][14][15], photolytic [16][17][18], electrolytic [19][20][21], and radiolytic [22][23][24][25] techniques to produce the tetraphenylboron radical. All of these studies show predominately both biphenyl and diphenylborinic acid as products.…”

Section: Wsrc-ms-98-00876 Rev 0 Page 5 Of 35mentioning

confidence: 99%

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Copper-catalyzed sodium tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid decomposition kinetic studies in aqueous alkaline solutions

Crawford

Barnes

Peterson

et al. 1999

Journal of Organometallic Chemistry

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This work studied the kinetics of copper-catalyzed decomposition of tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid (NaTPB, 3PB, 2PB and 1PB, respectively) in aqueous alkaline solution over the temperature range of 25 to 70 °C. The statistically designed test matrices added copper sulfate to maximum concentrations of 10 mg/L. The relative rates of decomposition increase in the order of NaTPB < 1PB ~ 3PB < 2PB. Dependence of decomposition on the amount of added copper increases in the order of 3PB ~ 2PB < 1PB ~ NaTPB. Activation energies ranged from 82 to 143 kJ/mole over the temperature range studied. Final decomposition products predominately involved benzene and phenol. All 3PB, 2PB and 1PB intermediate phenylborate species proved relatively stable (< 8% decomposition ) thermal hydrolysis of the phenylborate species occurs at 55 to 70° C in alkaline (0.6-2.3 M OH -, 2-4.7 M Na + ) solution with no added copper. The experiments suggest an important role for oxygen in copper-catalyzed phenylborate decomposition. NaTPB decomposes promptly under anoxic conditions while 3PB, 2PB and 1PB decompose faster in aerobic solutions. Benzene and phenol form as the predominant end-products from alkaline copper catalysis in static systems sealed under air. Both 2PB and 1PB decompose with near equal rates and quantitatively produce phenol under flowing air-purge conditions at 25 to 60 °C. Mechanisms for copper-catalyzed phenylborate decomposition likely involve a redox process giving loss of a phenyl group from the phenylborate with reduction of cupric ion, or dephenylation by reduced cuprous ion involving a phenylated copper intermediate.

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“…18,19 Further, Samec et al have proposed from irradiation experiments at 270 nm with a 150 W xenon arc lamp that the transferring species is a long-lived intermediate, formed during photochemical decomposition. 12 In the present work, unlike the above studies, the irradiation was performed by using a laser beam containing a major line at 325 nm and several minor lines from 220 to 275 nm, as previously mentioned.…”

Section: Tphbmentioning

confidence: 99%

Ultraviolet Laser Photo-Modulation Voltammetry of Tetraphenylborate at a Liquid/Liquid Interface

2005

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Photo-modulation voltammetry was applied to detecting the photolysis of tetraphenylborate (TPhB -) at a water/1,2-dichloroethane (DCE) interface by using a He-Cd laser emitting a beam with a major 325-nm line and minor lines of shorter wavelengths. When the interface was irradiated from the water-phase side, a new wave appeared in the photomodulation voltammogram, suggesting that TPhB -was photolyzed and the anionic product was transferred across the interface. The concentration dependence of the photocurrents was successfully explained by a theory based on the photolytic process at the interface.

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Boron photochemistry. I. Irradiation of sodium tetraarylborates in aqueous solution

Cited by 83 publications

References 0 publications

Evidences of Electron Transfer of a Fullerene Anion Radical (C60•-) Prepared under Visible-Light Illumination at a Nitrobenzene/Water Interface

Evidences of Electron Transfer of a Fullerene Anion Radical (C60•-) Prepared under Visible-Light Illumination at a Nitrobenzene/Water Interface

Copper-catalyzed sodium tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid decomposition kinetic studies in aqueous alkaline solutions

Ultraviolet Laser Photo-Modulation Voltammetry of Tetraphenylborate at a Liquid/Liquid Interface

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