- Preferential Solvation of Ag(I) Bromate and Iodate in Dimethyl Sulfoxide-Water Mixtures
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The selective solvation of Ag(I) bromate and iodate was studied in dimethyl sulfoxide-water mixtures at 30 deg C by solubility and EMF measurements.The solubility of silver bromate decreases down to XDMSO=0.2 and thereafter increases with addition of dimethyl sulfoxide, the solubility of silver iodate continuously decreasing under the same conditions.The transfer free energy of silver cation decreases while that of halate ions increases with the addition of dimethyl sulfoxide.The solvent transport number, Δ, passes through a maximum around XDMSO=0.5 in both cases.These results were interpreted in terms of a heteroselective solvation of both the salts, the silver ion being preferentially solvated by dimethyl sulfoxide and the halate ions selectively hydrated by water in the mixtures.
- Janardhanan, Sivasankaran nair,Kalidas, Chatty
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- Second-sphere coordination complexes via hydrogen bonding: Synthesis, characterization of [Co(NH3)6](XO3)3·nH2O (X=Br, I) and single crystal X-ray structure determination of [Co(NH3)6<
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Single crystals of [Co(NH3)6](BrO3)3·0.5H2O and peach coloured precipitate of [Co(NH3)6](IO3)3·3H2O were obtained by reacting hexaamminecobalt(II
- Sharma, Raj Pal,Bala, Ritu,Sharma, Rajni,Perez, Julio,Miguel, Daniel
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- Lewis acid promoted reactions. IV. Oxidation deprotection of trimethylsilyl ethers with silver and sodium bromates; AgBrO3, NaBrO3
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Primary and secondary benzylic and saturated trimethylsilyl ethers are converted to their carbonyl compounds with AgBrO3/AlCl3 efficiently. p-Hydroquinonetrimethylsilyl ether is also converted with both AgBrO3/AlCl3 and NaBrO3/AlCl3 to p-benzoquinone. AgBrO3/AlCl3 is also able to oxidize primary trimethylsilyl ethers to their carboxylic acids. Primary and secondary benzylic trimethylsilyl ethers are also converted to their carbonyl compounds with NaBrO3/AlCl3; AgBrO3 is more efficient and selective oxidant than NaBrO3.
- Firouzabadi,Mohammadpoor-Baltork
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p. 1065 - 1077
(2007/10/02)
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- Hydrates of Organic Compounds. VII. The Effect of Anions on the Formation of Clathrate Hydrates of Tetrabutylammonium Salts
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Phase diagrams of the binary mixtures of tetrabutylammonium salt nX (X = NO2, NO3, BrO3, ClO3, IO3, ClO4, MnO4, and NCS for n = 1; X = CO3, SO4, WO4, and CrO4 for n = 2; and X = PO4 for n = 3) with water were determined over the temperature range between -10 and +50 deg C.From these diagrams the following results were obtained: (1) the formation of a clathrate-like hydrate for salts having such anions as NO2-, NO3-, BrO3-, ClO3-, IO3-, SO42- and PO43- was newly confirmed; (2) the melting point of the clathrate hydrate of the salt with monovalent anion was appreciably influenced by the kind of anion; (3) in the hydrates of the salt having either di- or trivalent anions, the melting points were relatively high and were only slightly affected by the kind of anion; (4) the crystal structure of these hydrates was essentially the same as that of the tetrabutylammonium fluoride hydrate, judging from the hydration numbers; (5) the solubilities in water of both permanganate and perchlorate were markedly lower than that of the iodide; and (6) in the thiocyanate system a phase separation into two liquid phases was observed at temperatures higher than +3.5 deg C.The effect of a monovalent anion on the stability of the clathrate hydrate was discussed in connection with the conventional partial molal volume of the anion.
- Nakayama, Haruo
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p. 877 - 880
(2007/10/02)
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