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1.
The dissociation constants of (CH3)3PbCl at 26°C in water and in methanol have been determined to be 0.51 mol/l and 4.65 x 10 -4 mol/l, respectively, from the variations of Pb NMR chemical shifts (by INDOR) with concentration. Chemical shifts to (CH3)4Pb have been obtained for (CH3)3PbCl, for solvated (CH3)3Pb+, and for a possible dimer [(CH3)3PbCl]2 formed in methanol.  相似文献   

2.
An improved synthetic route to [210Pb]-(CH3)3PbCl is described in which chelated 210Pb2+ is methylated to [210Pb]-(CH3)4Pb with methylmagnesium bromide (CH3MgBr) in the presence of methyl iodide. Controlled oxidation of the product with anhydrous hydrochloric acid and purification of the crude product by reversed-phase high-pressure liquid chromotography (HPLC) resulted in [210Pb]-(CH3)3PbCl in 71% radiochemical yield. Whereas storage of the purified product at ?10 °C resulted in complete conversion to Pb2+ during one year, storage in 20% acetic acid at 4 °C resulted in less than 15% decomposition during six months. Periodic complexometric extractions to remove 210Pb radioactive daughters (210Bi, 100% β, Emax = 1.16 MeV; 210Po, 100% α, E = 5.305 MeV) from the storage solution did not alter the rate of decomposition. The rate of translocation of [210Pb]-(CH3)3Pb+ across an isolated tomato cuticle was approximately twice the rate of transfer of inorganic lead(II) and was not influenced by the presence of increasing amounts of disodium ethylenediamine-tetra-acetate.  相似文献   

3.
Crown Ether Complexes of Lead(II). The Crystal Structures of [PbCl(18-Krone-6)][SbCl6], [Pb(18-Krone-6)(CH3CN)3][SbCl6]2 und [Pb(15-Krone-5)2][SbCl6]2 . [PbCl(18-crown-6)][SbCl6] has been prepared in low yield besides [Pb(CH3)2(18-crown-6)][SbCl6]2 by the reaction of Pb(CH3)2Cl2 with antimony pentachloride in acetonitrile solution in the presence of 18-crown-6, forming pale-yellow crystals. The other two title compounds are formed as colourless crystals by the reaction of PbCl2 with antimony pentachloride in acetonitrile solutions in the presence of 18-crown-6 and 15-crown-5, respectively. The complexes were characterized by IR spectroscopy and by crystal structure determinations. [PbCl(18-crown-6)][SbCl6]: Space group P21/c, Z = 8, 5 003 observed unique reflections, R = 0.046. Lattice dimensions at - 80°C: a = 1 386.9; b = 1 642.7; c = 2 172.1 pm, β = 92.95°. The lead atom in the cation [PbCl(18-crown-6)]+ is surrounded in an almost hexagonal-planar construction by the six oxygen atoms of the crown ether and an axially oriented Cl atom. [Pb(18-crown-6)(CH3CN)3][SbCl6]2: Space group P1 , Z = 2, 6 128 observed unique reflections, R = 0.076. Lattice dimensions at - 70°C: a = 1 228.0; b = 1 422.9; c = 1 463.2 pm, α = 69.08°; β = 65.71°; γ = 64.51°. In the cation [Pb(18-crown-6)(CH3CN)3]2+ the lead atom is coordinated by the six oxygen atoms of the crown ether and by the three nitrogen atoms of the acetonitrile molecules. The structure determination is restricted by disorder. [Pb( 15-crown-5)2][SbCI6]2: Space group P63/m, Z = 6, 5 857 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = b = 2 198.5; c = 1499.4 pm, α = β = 90°, γ = 120°. In the cation [Pb(l5-crown-5)2]2 the lead atom is sandwich-like coordinated by the ten oxygen atoms of the two crown ether molecules. The structure determination is restricted by disorder.  相似文献   

4.
The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of +2-butanol (2BU, CH3CH2CH(OH)CH3) and 2-pentanol (2PE, CH3CH2CH2CH(OH)CH3). 2BU and 2PE react with OH yielding bimolecular rate constants of (8.1±2.0)×10−12 cm3molecule−1s−1 and (11.9±3.0)×10−12 cm3molecule−1s−1, respectively, at 297±3 K and 1 atmosphere total pressure. Both 2BU and 2PE OH rate constants reported here are in agreement with previously reported values [1–4]. In order to more clearly define these alcohols' atmospheric reaction mechanisms, an investigation into the OH+alcohol reaction products was also conducted. The OH+2BU reaction products and yields observed were: methyl ethyl ketone (MEK, (60±2)%, CH3CH2C((DOUBLEBOND)O)CH3) and acetaldehyde ((29±4)% HC((DOUBLEBOND)O)CH3). The OH+2PE reaction products and yields observed were: 2-pentanone (2PO, (41±4)%, CH3C((DOUBLEBOND)O)CH2CH2CH3), propionaldehyde ((14±2)% HC((DOUBLEBOND)O)CH2CH3), and acetaldehyde ((40±4)%, HC((DOUBLEBOND)O)CH3). The alcohols' reaction mechanisms are discussed in light of current understanding of oxygenated hydrocarbon atmospheric chemistry. Labeled (18O) 2BU/OH reactions were conducted to investigate 2BU's atmospheric transformation mechanism details. The findings reported here can be related to other structurally similar alcohols and may impact regulatory tools such as ground level ozone-forming potential calculations (incremental reactivity) [5]. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 745–752, 1998  相似文献   

5.
The synthesis and single-crystal x-ray structure determination of two new trinuclear metal complexes is detailed. In these we utilise the appended iminodiacetate substituents, in [Co(CH3)NH(CH2CO2H)2sar]3+, to act as a focus for coordination of other metal ions. Thus, we have made complexes of Cu and Ni utilising the basic carbonates of these metals and [Co(CH3){N(CH2CO2H)2}sar]3+ (CoL2) which gave rise to ((CoL2–2H+)2M), M = Cu and Ni. The electrochemical study of the latter was inconclusive and provides the impetus for further study.  相似文献   

6.
The chemical kinetics, studied by UV/Vis, IR and NMR, of the oxidative addition of iodomethane to [Rh((C6H5)COCHCOR)(CO)(PPh3)], with R = (CH2)nCH3, n = 1-3, consists of three consecutive reaction steps that involves isomers of two distinctly different classes of RhIII-alkyl and two distinctly different classes of RhIII-acyl species. Kinetic studies on the first oxidative addition step of [Rh((C6H5)COCHCOR)(CO)(PPh3)] + CH3I to form [Rh((C6H5)COCHCOR)(CH3)(CO)(PPh3)(I)] revealed a second order oxidative addition rate constant approximately 500-600 times faster than that observed for the Monsanto catalyst [Rh(CO)2I2]. The reaction rate of the first oxidative addition step in chloroform was not influenced by the increasing alkyl chain length of the R group on the β-diketonato ligand: k1 = 0.0333 ([Rh((C6H5)COCHCO(CH2CH3))(CO)(PPh3)]), 0.0437 ([Rh((C6H5)COCHCO(CH2CH2CH3))(CO)(PPh3)]) and 0.0354 dmmol−1 s−1 ([Rh((C6H5)COCHCO(CH2CH2CH2CH3))(CO)(PPh3)]). The pKa and keto-enol equilibrium constant, Kc, of the β-diketones (C6H5)COCH2COR, along with apparent group electronegativities, χR of the R group of the β-diketones (C6H5)COCH2COR, give a measurement of the electron donating character of the coordinating β-diketonato ligand: (R, pKa, Kc, χR) = (CH3, 8.70, 12.1, 2.34), (CH2CH3, 9.33, 8.2, 2.31), (CH2CH2CH3, 9.23, 11.5, 2.41) and (CH2CH2CH2CH3, 9.33, 11.6, 2.22).  相似文献   

7.
Thiophosphinate Complexes of Lanthanides. I. Dimeric Dimethylthiophosphinate Compounds of LaIII, PrIII, NdIII, and ErIII By reaction of Na[(CH3)2POS] · 1,5 H2O with Ln(ClO4)3 (Ln ? La, Pr, Nd, Er) neutral dimeric complexes are formed. The crystal and molecular structures of [Pr((CH3)2POS)3(C2H5OH)(C3H7OH)]2, [Pr((CH3)2POS)3 · 3 H2O]2 · 4 H2O and [Er((CH3)2POS)3(H2O)2]2 have been determined by single crystal X-ray crystallography. The (CH3)2POS? ions are acting partly as bidentate chelates and partly as monodentate O-donors. The dimers are formed by doubly coordinating oxygen atoms of two ligands. Very strong intramolecular O? H…?S hydrogen bonds exist between noncoordinated S atoms and coordinated water molecules.  相似文献   

8.
1,3-Dimethyl-2-imidazolidinone (dimethylethylene urea, DMEU) and 1,3-di- methyl-3,4,5,6-tetrahydro-2(IH)-pyrimidinone (dimethylpropylene urea, DMPU) adducts of the type Ph3SnX·L (X = Cl, Br and I), Ph3PbX·L (X = Br, I), 3Ph3PbCl·2DMEU and 2Ph3PbCl · DMPU have been prepared and characterized. Assignments are made for ν(CO) and ν(CN) frequencies in the IR, and for skeletal frequencies observed in both the IR and Raman spectra in the range 400 to 100 cm?1 Infrared measurements show that the adducts are bound through the carbonyl oxygen, and are highly dissociated in dichloromethane solution. 1H and 119Sn or 207Pb NMR measurements reveal that ligand exchange, fast on the NMR time scale, occurs in solution. Coordination of the ligand causes a large upfield shift in the 119Sn or 207Pb resonances, but Ph3MI · L have shifts similar to those for the parent iodides, indicating almost complete dissociation. Thermodynamic parameters are reported for the dissociation of Ph3SnX · DMPU (X = Cl, Br) in CH2Cl2 solution.  相似文献   

9.
李纲  李子峰  吴静霞  王利鹏  侯红卫 《化学学报》2007,65(14):1363-1367
Pb(OAc)2•3H2O, 3-二茂铁-2-丁烯酸钠以及1,10-邻菲啰啉在甲醇中反应得到了铅的配位聚合物: [Pb(m-OOCCH=C(CH3)Fc)(m2-OOCCH=C(CH3)Fc)(phen)]n (Fc=(h5-C5H5)Fe(h5-C5H4); phen=1,10-邻菲啰啉). 单晶测试表明: 每个铅离子为六配位, 其中4个氧原子来自4个3-二茂铁-2-丁烯酸根, 另2个氮原子来自邻菲啰啉; 相邻的铅离子通过3-二茂铁-2-丁烯酸根的单齿和双齿氧原子桥连形成了一个无限的一维长链. 研究了标题化合物在DMF溶液中的电化学性能.  相似文献   

10.
In order to check the hypothesis that rubratoxin B ( 2 ), a C26-metabolite, is formed biogenetically by head-to-tail coupling of two identical C13-precursors derived from decanoic acid and oxaloacetic acid, two labelled forms of the postulated C13-intermediate 2-((E)-1'-octenyl)-3-[14C]methyl- and 2-((E)-1'-octenyl)-3-[13C]-methylmaleic anhydride ( 10 ), were synthesized. The labelled compounds 10 as well as a number of other 14C]- and [13C]-labelled potential precursors were administered to growing cultures of Penicillium rubrum STOLL . Significant incorporation rates of acetate (as intact units) and malonate were observed. Propionate was incorporated after decarboxylation. Succinate exhibited the highest rate of incorporation. The results are in agreement with the assumption that the C10-chain is formed by the fatty acid pathway and the C3-unit via the tricarboxylic acid cycle. After administration of 10 randomization of the label was observed. Thus the question whether compound 10 is a biogenetic intermediate remains unanswered.  相似文献   

11.
Two pseudohalide thiocyanate ions (SCN?) have been used to replace two iodides in CH3NH3PbI3, and the resulting perovskite material was used as the active material in solar cells. In accelerated stability tests, the CH3NH3Pb(SCN)2I perovskite films were shown to be superior to the conventional CH3NH3PbI3 films as no significant degradation was observed after the film had been exposed to air with a relative humidity of 95 % for over four hours, whereas CH3NH3PbI3 films degraded in less than 1.5 hours. Solar cells based on CH3NH3Pb(SCN)2I thin films exhibited an efficiency of 8.3 %, which is comparable to that of CH3NH3PbI3 based cells fabricated in the same way.  相似文献   

12.
The electrochemical properties of electrolyte for soluble lead flow battery(SLFB) are a key factor for the improvement of its performance. Pb(BF4)2 in which Pb2+ ions are highly soluble is cheaper and more stable than conventional Pb(CH3SO3)2. This paper presents the electrochemical properties of HBF4 and Pb(BF4)2 prepared with recovered lead for the electrolytes of SLFB. The density difference of reagent grade and recovered lead electrolytes is less than 0.05 g/cm3 and their viscosities increase up to 132 %, 120 %, respectively when concentration of Pb(BF4)2 changes from zero to 2.0 mol·dm−3. The conductivity of 1.5 mol·dm−3 electrolyte prepared with recovered lead has a peak when concentration of HBF4 is less than 1.0 mol·dm−3. The results of cyclic voltammetry, linear sweep voltammetry and constant current charge/discharge test showed that impurities of recovered lead exert insignificant influences on the Pb2+/Pb and Pb2+/PbO2 reactions. These results are promising to apply recovered lead to SLFB.  相似文献   

13.
For synthetic studies the protection of the hydroxyl groups of phomin (cytochalasin B) ((7S,22R,26R)-7,26-dihydroxy-22-methyl-30-oxa-[14]cytochalasa-6(18), 19t 27t-trien-1,29-dion) ( 1 ), the dodecahydro-derivative 2 , and the dihydro-derivative 4 by methylation was investigated. Treatment of 1 with CH3I/Ag2O gave the iminoether 6 . The reaction of 4 with CH2N2/BF3 led to the di-O-methyl derivative 8 and to the N-methyl-di-O-methyl derivative 9 , whereas 2 was transformed to the N-methyl-di-O-methyl compound 10 and to the iminoether 11 . NaBH4 reduction of 3 yielded not only 4 but also the epimeric dihydro derivative 5 .  相似文献   

14.
Inhaltsübersicht. Trimethylamin und Antimon(V)-chlorid bilden keinen Dornor-Acceptor Komplex. In Abhängigkeit vom Molverhältnis reagieren die Komponenten zu (CH3)3NCl+SbCl6 (I) bzw. zu (CH3)3NH+X und (CH3)2N=CH3+X (X = SbCl6, SbCI4, Sb3CI143– und CI). I kann in (CH3)3NH+SbCl6 und (CH3)2N=CH2+SbCl6 zerfallen. The Reaction of Trimethylamine with Antimony (V) Chloride Abstract. Trimethylamine and antimony(V) chloride forms no donor-acceptor-complex. In dependence of the molar ratio the compounds reacts to (CH3)3NCl+SbCl6 (I) resp. to (CH3)3NH+X and (CH3)2N=CH3+X (X = SbCl6, SbCI4, Sb3CI143– and CI). I can decompose into (CH3)3NH+SbCl6 and (CH3)2N=CH2+SbCl6.  相似文献   

15.
The 13P and 13C spectra of the triply 13C labelled molecules (CH3)3P, (CH3)3PO, (CH3)3PS and (CH3)3PSe oriented in a nematic phase are reported. The CPC bond angles have been measured. The 13P chemical shift tensor shows a large anisotropy except in the case of (CH3)3P. The abnormal large value observed for the PSe bond length suggests a large anisotropy of the 1J(PSe) spin coupling.  相似文献   

16.
A series of [M(CO)5I] and [M2(CO)10I] anion complexes have been synthesized by the photochemical reaction of PhCH2N(CH3)3I or FcCH2N(CH3)3I (Fc=ferrocenyl) with M(CO)6 (M = Cr, Mo or W), and characterized by elemental analyses, i.r., 1H-n.m.r. and 13C-n.m.r. spectra in the case of the molybdenum and tungsten complexes. These complexes exhibit considerably different electrochemical behavior, when investigated by cyclic voltammetry. The crystal structures of [PhCH2N(CH3)3][Cr(CO)5I] and [FcCH2N(CH3)3][W2(CO)10I] have been determined by X-ray diffraction, indicating that only weak contacts maybe exist between anions and cations by the I...H bond in the former, and there are no direct interactions between anions and cations in the latter.  相似文献   

17.
Two triangular molybdenum‐tellurium clusters, Mo3Te7‐[S2CN (CH2CH2OH2]3I (1) and Mo3Te4Y3[S2P(iPrO)2]3I (Y3 = 1. 43Te+ 1.57S) (2), were obtained from the reaction of K · HOdtc [HOdtc = S2CN(CH2CH2OH)2] or K·iPr2dtp (iPr2dtp = S2P[OCH(CH3)2]2) with a mixed product of elements Mo, Te(S) and I2 at high temperature. The structures of the two compounds were determined by X‐ray crystallography study. Crystal data are, (1): monoclinic, P21/n, a = 1.6256(3), b = 1.3264(2), c = 1.8808(4) nm, β=96.923°, V = 4.025.9 (14) nm3, Dcal = 3.050g·cm‐3, Z = 4, and (2): monoclinic, P21/n, a = 1.4564(2), b = 2.3917(4), c = 1.5094(3) nm, β = 114.35(2)°, V = 4.0259(14) nm3, Dcal = 2.449 g·cm?3 and Z = 4. Single crystal analyses show that 1 consists of discrete Mo3Te7[S2CN(CH2CH2OH)2]3I connected into three‐dimensional framework via hydrogen bonds, while 2 forms a linear chain via Te(S)—I interaction.  相似文献   

18.
Rate constants for a series of alcohols, ethers, and esters toward the sulfate radical (SO4?) have been directly determined using a laser photolysis set‐up in which the radical was produced by the photodissociation of peroxodisulfate anions. The sulfate radical concentration was monitored by following its optical absorption by means of time resolved spectroscopy techniques. At room temperature the following rate constants were derived: methanol ((1.6 ± 0.2) × 107 M?1 s?1); ethanol ((7.8 ± 1.2) × 107 M?1 s?1); tert‐butanol ((8.9 ± 0.3) × 105 M?1 s?1); diethyl ether ((1.8 ± 0.1) × 108 M?1 s?1); MTBE ((3.13 ± 0.02) × 107 M?1 s?1); tetrahydrofuran (THF) ((2.3 ± 0.2) × 108 M?1 s?1); hydrated formaldehyde ((1.4 ± 0.2) × 107 M?1 s?1); hydrated glyoxal ((2.4 ± 0.2) × 107 M?1 s?1); dimethyl malonate (CH3OC(O)CH2C(O)OCH3) ((1.28 ± 0.02) × 106 M?1 s?1); and dimethyl succinate (CH3OC(O)CH2CH2C(O)OCH3) ((1.37 ± 0.08) × 106 M?1 s?1) where the errors represent 2σ. For the two latter species, we also measured the temperature dependence of the corresponding rate constants. A correlation of these kinetics with the bond dissociation energy is also presented and discussed. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 539–547, 2001  相似文献   

19.
The reactions of the aluminium halides AlCl3, AlBr3, and AlI3 (I, II, III) with the trimethylsilylorganylsulfides (CH3)3 SiSCH3, (CH3)3 SiSC2H5, and (CH3)3 SiSPh (IV, V, VI), as well as the lead bis(thiolates) Pb(SCH3)2, Pb(SC2H5)2, Pb(S-i- C3H7)2, and Pb(SPh)2 (XV, XVI, XVII, XVIII) and the redox reactions between III and the organic disulfides CH3SSCH3 and PhSSPh (XXIX, XXX) have been investigated. In benzene solution the reactions of I, II and III with IV, V and VI yield the 1:1 adducts, the aluminium trihalide · trimethylsilylorganylsulfides VII–XIV. By heating under vacuum these adducts form the corresponding organylthioaluminium dihalides. These compounds are obtained as well by the reaction of I, II, and III with XV, XVI, XVII and XVIII. The redox reactions between III and the disulfides XXIX and XXX also lead to the corresponding organylthioaluminium diiodides.The spectra and some physical and chemical properties of the new compounds are described.  相似文献   

20.
The reactivity of the carbanion (CH2CO2Et)?, obtained from CH2(Br)CO2Et (I) by means of electrochemical reduction, on substrates such as CH2(Br)CH2CO2Et (II), CH2(Br)(CH2)2CO2Et (III) and CH2(Br)(CH2) 3CO2Me (IV), was studied in dimethylformamide solutions by means of polarography, cyclic voltammetry and coulometry at mercury and vitreous carbon electrodes. Evidence was found for coupling (diethyl glutarate (CH2)3(CO2Et)2 and diethyl adipate (CH2)4(CO2Et)2) and elimination reaction (ethyl acrylate CH2CHCO2Et and ethyl cyclopropancarboxylate CH2CH2CHCO2Et) compounds. In addition, the electrochemical reduction of the single esters (I)–(IV) was reported. The dependence of the percentage ratio among the various products obtained on the potential, the proton donor presence and the nature of the ester were investigated.  相似文献   

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