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One unit of S(IV) (SO2 or SHO3?) is oxidized per 2 units of [NiIII(cyclam)] species to obtain sulfate. Kinetic analyses have been done by varying the acidities (0.013 ? [H+] ? 1.0 M) and halide concentrations (0.000 ? [X?] ? 0.012 M; X=Cl and Br) at constant ionic strength (μ = 1.0 M). The rate law that incorporates the [X?] and [H+] dependence is ?d[NiIII]T/dt=2k[NiIII]T[S(IV)]T where 2k={ka[H+] + kbK + kK′X[H+] [X?] + kK′XK[X?]} {[H+] + K}?1 {1 + K′X[X?]}?1, here ka=87 ± 7 M?1 s?1, kb=(2.5 ± 0.5)×103 M?1 s?1 and pK = 1.8 ± 0.2. Rate constants ka and kb are attributed to the reactions of [NiIII(cyclam) (H2O)2]3+ with SO2 and SHO3?, respectively. Monohalo species apparent equilibrium constants K′Cl=(1600 ± 400) M?1 and K′Br=(190 ± 20) M?1 and rate constants k=80 ± 8 M?1 s?1 and k = 140 ± 15 M?1 s?1 are ascribed to the protonated pathway, involving the [NiIII(cyclam) (H2O)X]2+ and SO2(aq) reaction pairs. The other two rate constants of k=(5 ± 1)×103 M?1 s?1 and k=(3.1 ± 0.5)×104 M?1 s?1, refer to the deprotonated pathway and are assigned to the [NiIII(cyclam) (H2O)X]2+ /SHO3? redox couple. A deuterium H2O / D2O isotope effect of 2.1–2.8 can be attributed partially to an equilibrium isotope effect at low acidity though a small kinetic isotope (2.5 ± 0.5) effect is evident for the dihydrogen sulfito pathway, ka. The kinetic isotope effect and the absence of sulfite radical scavenging effects are explained by a mechanism entailing migration of a hydride from sulfur to the NiIII center to produce a NiIII—H species, which rapidly comproportionates, and S(VI). © 1993 John Wiley & Sons, Inc. 相似文献
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A study of the preparations of the complex hydridic anions [MH(6)](4)(-) (M = Fe and Ru) reveals a number of distinctive features. Here a soluble homoleptic ruthenium hydride has been prepared for the first time. For example, both FeX(2) and [Ru(eta(4)-1,5-COD)X(2)], X = Cl and Br, react with PhMgBr solutions under hydrogen to produce the title compounds. The benzene liberated in these reactions is more readily hydrogenated in the case of a homogeneous room temperature ruthenium hydride preparation to both cyclohexane and cyclohexene. The (1)H NMR spectroscopic data show that the two complex anions have hydride absorptions in the low-frequency region, delta -20.3 and -14.7, respectively. Further, (1)H spin-lattice relaxation times (T(1)) for M-H are longer in the case of Ru vs Fe. 相似文献
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Electron paramagnetic resonance (EPR) spectra of powder and oriented films of montmorillonite, hectorite, and saponite intercalated with [Cu(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) exhibit three components: an orientation-dependent component without hyperfine features, an orientation-dependent component with hyperfine features, and an orientation-independent component without hyperfine feature. EPR spectra of [Cu(cyclam)](2+)-saponite, which exhibit only two components and the best resolved hyperfine features, were simulated. The spectra indicate that a large portion of the saponite platelets are inclined to the glass surface, although they tend to align with their basal planes parallel to the glass surface. The orientation-dependent spectra could be simulated by introducing a Gaussian distribution with a standard deviation of 20 degrees for the inclination angle. The standard deviation may be used as a disorder parameter for the microcrystals assembled on glass plates. Spectral simulation also shows that the CuN(4) plane of [Cu(cyclam)](2+) is parallel to the clay layers. EPR spectra of some other partially oriented systems are also discussed. 相似文献
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Gerritz SW Norman MH Barger LA Berman J Bigham EC Bishop MJ Drewry DH Garrison DT Heyer D Hodson SJ Kakel JA Linn JA Marron BE Nanthakumar SS Navas FJ 《Journal of combinatorial chemistry》2003,5(2):110-117
The high-throughput manual solid-phase parallel synthesis of libraries comprising thousands of discrete samples using pellicular supports (i.e. SynPhase crowns and lanterns) and a suite of novel tools and techniques is described. Key aspects of this approach include the combination of a split-split-split synthesis strategy with spatial encoding to differentiate thousands of crowns, the rapid washing and filtration of up to 48 reaction vessels in parallel, the application of an inexpensive and environmentally friendly technique to remove trifluoroacetic acid from sixteen 96-well plates in parallel, and a high-throughput method for removing cleaved crowns from reusable pin racks. Tens of thousands of discrete samples have been produced in-house using this conceptually and operationally straightforward strategy. 相似文献
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Ohne Zusammenfassung 相似文献
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Linn I. Sennott 《Mathematical Methods of Operations Research》1997,45(1):45-62
The Approximating Sequence Method for computation of average cost optimal stationary policies in denumerahle state Markov decision chains, introduced in Sennott (1994), is reviewed. New methods for verifying the assumptions are given. These are useful for models with multidimensional state spaces that satisfy certain mild structural properties. The results are applied to four problems in the optimal routing of packets to parallel queues. Numerical results are given for one of the models. 相似文献