- Dithizone Adsorption at Metal Electrodes. 2. Raman Spectroelectrochemical Investigation of Effect of Applied Potential at a Silver Electrode
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The technique of laser Raman spectroelectrochemistry has been applied to the study of the adsorption of the diphenylthiocarbazone (dithizone) anion and its redox forms at a silver electrode in aqueous alkaline media.Raman spectra of the adsorbed forms of
- Pemberton, Jeanne E.,Buck, Richard P.
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- Chemical and electrochemical oxidation and reduction of dithizone
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A non-aqueous electrochemical study of dithizone, H2Dz, 1, is compared with the chemical oxidation and reduction profile of this versatile ligand. Chemical oxidation of 1 by I2 initially leads to an isolatable disulfide-bridged species, (HDz)2, 22, but ultimately monomeric dehydrodithizone, Dz, 3, is formed. Electrochemically, in CH2Cl2/0.1 mol dm-3 [N(nBu)4][B(C6F5)4], two oxidation processes are observed for 1. Evidence of the electrochemical formation of the dimer 22 was found, but on a CV timescale the fully oxidized species, 22 oxidized, did not convert to the chemically stable species 3. Regeneration of 1 during an irreversible electrochemical reduction of the electrochemically generated fully oxidized species, 22 oxidized, was detected. Two further one-electron electrochemical irreversible reduction steps were also identified to ultimately generate H3Dz-, 8, one of the synthetic precursors to 1. In contrast, resolution and identification of the electron transfer steps of 1 in both dimethylsulfoxide, DMSO, or in CH2Cl2/0.1 mol dm-3 [N(nBu)4][PF6] were hampered by solvation and ion paring of [PF6]- especially with the oxidized species of 1. A metathesis of water-soluble potassium dithizonate, KHDz, 4b, led to lipophilic [N(nBu)4][HDz], 4c.
- von Eschwege, Karel G.,Swarts, Jannie C.
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experimental part
p. 1727 - 1733
(2010/07/04)
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- Synthesis of 2,3-diaryltetrazole-5-thiones and theoretical studies on atomic charge distributions of 2,3-diphenyltetrazole-5-thione
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Four 2,3-diaryltetrazole-5-thiones have been synthesized in high yields using a new synthetic method under mild reaction conditions. Theoretical calculations of the structure, vibrational frequencies, and natural population analysis (NPA) of atomic charge
- Jian, Fangfang,Zhao, Pusu,Zhang, Lan,Hou, Yuxia
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p. 8322 - 8326
(2007/10/03)
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- Preferential solvation and molecular orbital calculation studies of solvatochromic mesoionic 2,3-diaryl-2H-tetrazolium-5-thiolate derivatives
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Solvent effects on the electronic spectra of some mesoionic 2,3-diaryl-2H-tetrazolium-5-thiolate derivatives were investigated in thirteen pure solvents and eight water-organic solvent mixtures. In pure solvents, the solvatochromic shifts of the mesoionic
- Taha,Kiwan
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p. 502 - 508
(2007/10/03)
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- Isomers of 3-Methylthio-1,5-diarylformazans and their Interconversion in Solution
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1H and 13C n.m.r. and i.r. spectroscopic studies, including 15N-labelling, on solutions of ArNNC(SR)NNHAr (Ar = Ph, p-, or o-tolyl; R = CH3 or CD3) taken in conjunction with established X-ray crystal structures of pure isomers have made it possible to est
- Hutton, Alan T.,Irving, Harry M. N. H.
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p. 1117 - 1122
(2007/10/02)
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- 3-Carboxymethylthio-1,5-diphenylformazan: a Potential Terdentate Ligand with Unusual Properties
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3-Carboxymethylthio-1,5-diphenylformazan (8), prepared by two synthetic routes as a potential terdentate ligand, is a very weak base (pK1= -0.43) and an exceptionally weak acid (pK2= 12.48) which does not yield metal complexes.No car
- Hutton, Alan T.,Irving, Harry M. N. H.
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p. 139 - 145
(2007/10/02)
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