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1.
2.
An O-bonded sulphito complex, Rh(OH2)5(OSO2H)2+, is reversibly formed in the stoppedflow time scale when Rh(OH2)
6
3+
and SO2/HSO
3
−
buffer (1 <pH< 3) are allowed to react. For Rh(OH2)5OH2++ SO2 □ Rh(OH2)5(OSO2H)2+ (k1/k-1), k1 = (2.2 ±0.2) × 103 dm3 mol−1 s−1, k−1 = 0.58 ±0.16 s−1 (25°C,I = 0.5 mol dm−3). The protonated O-sulphito complex is a moderate acid (K
d
= 3 × 10−4 mol dm−3, 25°C, I= 0.5 mol dm−3). This complex undergoes (O, O) chelation by the bound bisulphite withk= 1.4 × 10−3 s−1 (31°C) to Rh(OH2)4(O2SO)+ and the chelated sulphito complex takes up another HSO
3
−
in a fast equilibrium step to yield Rh(OH2)3(O2SO)(OSO2H) which further undergoes intramolecular ligand isomerisation to the S-bonded sulphito complex: Rh(OH2)3(O2SO)(OSO2)- → Rh(OH2)3(O2SO)(SO3)− (k
iso
= 3 × 10−4 s−1, 31°C). A dinuclear (μ-O, O) sulphite-bridged complex, Na4[Rh2(μ-OH)2(OH)2(μ-OS(O)O)(O2SO)(SO3) (OH2)]5H2O with (O, O) chelated and S-bonded sulphites has been isolated and characterized. This complex is sparingly soluble in water
and most organic solvents and very stable to acid-catalysed decomposition 相似文献
3.
Summary The reversible complex formation between oxalatopentaammine cobalt(III), aluminium(III) and gallium(III) was investigated by the stopped flow technique at 30 ± 0.1 °C and I = 1.0 mol dm–3. The reactivity sequence: GaIII > AlIII is observed, however, the major path for gallium(III) was (NH3)5CoC2O4H2+ + GaOH2+ (NH3)5CoC2O4-Ga4+ + H2O. The formation and dissociation rate constants of the binuclear species have been compared with the analogous data for iron(III) and nickel(II) reported earlier. The results reflect the fact that the half-bonded exalato moiety of (NH3)5CoC2O
inf4
p+
acts as a chelating agent for the metal ions.Author to whom all correspondence should be directed. 相似文献
4.
A rapid access to 7-azaspiro[4.5]decan-6-ones 1 involving three regio- and chemoselective reactions starting from tetrabromonorbornyl derivatives is described. The alkaline H(2)O(2) cleavage reaction of monosubstituted alpha-diketones 9 furnished the potential bridged bicyclic lactones 10in a highly regio- and stereoselective manner. The radical-mediated, intermolecular bridgehead C-C bond formation of the versatile bridged lactones 10 with acrylonitrile followed by LAH reduction of the adduct 13 intriguingly leads to the formation of novel spirolactam building blocks 1. 相似文献
5.
Upendra Nath Dash Banka Behari Das Uttam Kumar Biswal Tapodhan Panda 《Thermochimica Acta》1984,80(2):331-342
The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X−, and the standard thermodynamic quantities for the transfer of 1 g-ion of X− from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag+ and Ag/AgX, X− electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures. 相似文献
6.
7.
The extraction behaviour of thorium(IV) from aqueous nitric acid employing 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) in the presence of tri-n-octyl phosphine oxide (TOPO) as well as tri-n-butyl phosphate (TBP) in xylene medium was investigated. The extraction constant (log k(ex)) for the binary organic phase species Th(PBI)(4) was determined to be 8.26 which is by far the largest amongst the corresponding values known for other beta-diketones. The overall extraction constant (log K) for the ternary species Th(PBI)(4) TBP and Th(PBI)(4).2TOPO were estimated to be 14.96 and 20.96 respectively. An inverse correlation of the adduct formation constant (log K(s)) with the pK(a) of the beta-diketones, 2-thenoyltrifluoroacetone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and HPBI, was observed. The steric as well as the electronic effects of adduct formation have been discussed. Analytical application of HPBI for the separation of (234)Th radiotracer from natural uranium (99.3% (238)U) has been suggested. 相似文献
8.
Flögel O Dash J Brüdgam I Hartl H Reissig HU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4283-4290
Addition of lithiated methoxyallene to pivalonitrile afforded after aqueous workup the expected iminoallene 1 in excellent yield. Treatment of this intermediate with silver nitrate accomplished the desired cyclization to the electron-rich pyrrole derivative 2 in moderate yield. Surprisingly, trifluoroacetic acid converted iminoallene 1 to a mixture of enamide 3 and trifluoromethyl-substituted pyridinol 4 (together with its tautomer 5). A plausible mechanism proposed for this intriguing transformation involves addition of trifluoroacetate to the central allene carbon atom of an allenyl iminium intermediate as crucial step. Enamide 3 is converted to pyridinol 4 by an intramolecular aldol-type process. A practical direct synthesis of trifluoromethyl-substituted pyridinols 4, 10, 11, and 12 starting from typical nitriles and methoxyallene was established. Pyridinol 10 shows an interesting crystal packing with three molecules in the elementary cell and a remarkable helical supramolecular arrangement. Trifluoromethyl-substituted pyridinol 4 was converted to the corresponding pyridyl nonaflate 13, which is an excellent precursor for palladium-catalyzed reactions leading to pyridine derivatives 14-16 in good to excellent yields. The new synthesis of trifluoromethyl-substituted pyridines disclosed here demonstrates a novel reactivity pattern of lithiated methoxyallene which is incorporated into the products as the unusual tripolar synthon B. 相似文献
9.
10.
The retention of 131I on ceramic rod coated with silver nitrate followed by coating with a polyurethane membrane to be applied in brachytherapy
was studied. The concentration of silver nitrate (20 g/l), the volume of 131I as a sodium iodide solution (100 μl), the pH of the reaction mixture (pH 9) etc., were optimized to get a maximum uptake
on the ceramic rod. The concentration of coating solution (5%, polyurethane in tetrahydrofuran) was also optimized to obtain
a minimum leaching of 131I activity in normal saline solution. After coating with a polyurethane membrane, the 131I absorbed on the ceramic rod exhibited low leachability (0.03%). This method can be applied for the preparation of 125I interstitial sources to be used in eye and prostate cancer therapy.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献