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61.
The new compound, Na[(Mo2
VO4)(pte)(OMe)(MeOH)2] (pte = anion of 6-acetonylisoxanthopterin), has been prepared using the redox non-innocent title ligand in MeOH–H2O, and characterized by elemental analysis and physico-chemical methods including e.s.m.s., i.r., u.v.–vis. and 1H-n.m.r. spectra. Rate constants data (1.4 × 10–3 s–1 at 300 K) for its oxygen atom transfer with dimethyl sulphoxide tally with those of synthetic analogue systems reported earlier by different authors. The negative activation entropy (–206.3 J mol–1 deg–1) is consistent with an associative mechanism for this reaction. 相似文献
62.
Paul I. Surjasasmita Ben S. Freiser 《Journal of the American Society for Mass Spectrometry》1993,4(2):135-144
In this paper we report an extension of our earlier study on the structure of Alfacetone)2 + Collision-induced dissociation (CID) on MfacetoneXacetone-d6)+ for M = Al, Fe, Co, and Cu yields primarily, if not exclusively, nearly equal amounts of acetone and acetone-d6. Likewise, infrared multiphoton dissociation (IRMPD) at 10.6 μm yields, exclusively, nearly equal losses of the labeled and unlabeled acetones. These results suggest that the two acetone ligands bind in an equivalent fashion. Sc+ was also studied, which proved to be the most interesting. Sc+ reacts with acetone to form primarily ScO+, which undergoes higher order reactions leading to several products including ScO(acetone)2 +. IRMPD on this ion produces ScO(acetone-d6)(CD2CO)+, while its perdeuterated analog also produces ScO(acetone-d6)+ in addition to ScO(acetone-d6(CD2CO)+. The IRMPD results are supplemented by studying the primary and higher order reactions of Sc+ with acetone, as well as the CID of ScO(acetone)2 +. Finally, a qualitative assessment of the infrared photodissociation cross sections is given. It is found that the relative photodissociation cross sections follow the orders Co(acetone-d6)2 + > Co(acetone)(acetone-d6) > Co(acetone)2 + and Co(acetone-d6)+ > Co(acetone)+. 相似文献
63.
Mohammad Ali Bigdeli Abbas Rahmati Hossein Abbasi-Ghadim Gholam Hossein Mahdavinia 《Tetrahedron letters》2007,48(26):4575-4578
Aromatic amines have been synthesized efficiently from enamines using SnCl4 and SbCl5 in CH2Cl2 at room temperature. 相似文献
64.
Sofiane Ben Hamouda Quang Trong Nguyen Pierre Schaetzel 《European Polymer Journal》2006,42(11):2994-3005
Ethylene/ethane sorption characteristics were determined for dry Pebax™ (poly(amide 12-block-tetramethylenoxide) copolymer)/AgBF4 membranes by using an electronic microbalance. The membranes containing 0.7 and 22 wt.% AgBF4 showed a dual-mode sorption isotherm. The ethane isotherms for all the membranes were of the Henry-type, which is the normal sorption for gases in rubbery polymers. The abnormal presence of Langmuir sorption sites only for ethylene in the rubbery copolymer, never reported sofar, is attributed to the silver-based specific complexation sites. The silver salt which dissolved in limited amounts in the rubbery copolymer had a much smaller Langmuir sorption capacity than the salt that crystallized in the copolymer. The sorption kinetics indicate that the crystallized salt did adsorb slowly ethylene according to a zeroth-order kinetics, but not ethane. The gas uptake kinetics resulting from a step of the pressure surrounding the copolymer exhibited one stage for ethane but two stages for ethylene. For the latter, there was first a fast Fickian sorption stage, then a drift of the zeroth-order sorption of ethylene on salt crystals, which contributes for a large part to the total uptake. The zeroth-order sorption suggests that the sorbed ethylene amount in the second-stage is independent of the crystal-surface coverage. The value of the Fickian diffusion coefficient calculated by fitting the kinetics with a solution of the second Fick’s law was 5 × 10−12 m2/s for both ethylene (the first stage) and ethane, and is typical for small organic compounds in a rubbery material. 相似文献
65.
Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC6H4NHSiEt3 compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO2, 18; p-CN, ca. 43; p-NO2, ca. 120. (ii) For PhNHSi(C6H4Y)3 compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR3 compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R3 =) Et3, 1.0; Et2Me, 18 (at 30°); Me2-i-Pr, 8 (at 30°);Me2-t-Bu, 0.012 (at 50°);i-Pr3, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed. 相似文献
66.
Mohammad Ali Zolfigol Iraj Mohammadpoor-BaltorkDavood Habibi BiBi Fatemeh MirjaliliAbdolhamid Bamoniri 《Tetrahedron letters》2003,44(44):8165-8167
Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H® with good to excellent yields under mild and heterogeneous conditions. 相似文献
67.
Brett Ammundsen Gary R. Burns Ali Amran Stig E. Friberg 《Journal of Sol-Gel Science and Technology》1995,4(1):23-29
The effects of thermal treatment on composite materials prepared by the gelation of sols comprising large concentrations of metal oxide precursor salts have been investigated, in order to determine the compositional and thermal requirements for forming spinel magnesium manganates in such systems. The preparative technique has been found to give rise to derived gel materials in which the metal oxide phase, in the form of regular spherical particles, is dispersed throughout a continuous silica matrix. Silica-supported mixed magnesium and manganese spinel oxide phases were obtained for systems comprising at least 30 wt% metal nitrate after heating to temperatures between 700 and 850°C, but not without concomitant formation of Mn2O3 and modification of the silica network by magnesium. 相似文献
68.
The thermal stability of the Schiff base ethylacetoacetate-o-chlorobenzylamine (bdII), N-o-chlorobenzyl-C-benzoyl acetamide (bdIII), and N-p-chlorobenzyl-C-benzoyl acetamide (bdIV) were studied by thermogravimetric analysis. II Gave N,N'-di(o-chlorobenzyl) urea (bdIa) at 60° C, whereas the thermogravimetric curves of III and IV indicate that reactions other than formation of I may occur. The urea derivatives (I) have also been prepared from benzylamines and the corresponding β-ketoester and identified. 相似文献
69.
The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE
1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E
1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE
1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi 相似文献
70.
Conway B Hevia E Kennedy AR Mulvey RE Weatherstone S 《Dalton transactions (Cambridge, England : 2003)》2005,(8):1532-1544
Synthesised either by an unusual tert-butyl metathesis between tert-butyllithium and a n,s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA (5)(DBA=dibenzylamide), Bu(t)MgDA (6)(DA=diisopropylamide), Bu(t)MgHMDS (7)(HMDS=1,1,1,3,3,3-hexamethyldisilazide), Bu(t)MgTMP (8)(TMP=2,2,6,6-tetramethylpiperidide) and Bu(t)MgNCy2 (9)(cy=cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)2 ring and terminal Bu(t) ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu(n)MgN(H)Dipp]12 (10a) and its monomeric solvate Bu(n)MgN(H)Dipp.TMEDA (10b)(Dipp=2,6-diisopropylphenyl; TMEDA=N,N,N',N'-tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu(t)MgOBu(t).THF (11), Bu(t)Mg(mu-OBu(t))(mu-TMP)MgTMP (12) and Mg(OBu(n))HMDS.solv [solv=THF (13a) or Et2O (13b)], made fortuitously during the course of this work, are also presented. 相似文献