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11.
The Chemistry of 10-Pn-3 Systems1: Tricoordinate Hypervalent Pnictogen Compounds and Related Systems
Anthony J. Arduengo III David A. Dixon Constantine A. Stewart 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):341-344
Abstract The unusual hypervalent tricoordinate pnictogen systems, 10-Pn-3 ADPnO, provide a convenient starting point for the study of a wide range of main group chemistry. Differences in reactivity patterns among the pnictogens are readily apparent from the variety of chemistry exhibited. The ADPnO systems also provide a model for the recently recognized edge inversion mechanism for 3 and 4 coordinate 8-electron main group species. 相似文献
12.
Constantine D. Papaspyrides 《高分子科学杂志,C辑:聚合物评论》2013,53(2):325-333
Abstract Unsaturated polyester resins are widely used in the field of chemical process equipment [1-4] because of their handling properties. For example, large structures of complex shape can be fabricated with simple tools, frequently on the site. In general, unsaturated polyesters do not show an outstanding resistance to strong solutions of corrosive chemicals in contrast with other plastics. Nevertheless, as the chemistry of the unsaturated polyesters developed, special resins were made with excellent resistance to chemicals while maintaining important handling properties. 相似文献
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Electronically modified PHOX ligands 3a-e were synthesized to probe the mechanism of the enantioselective palladium-catalyzed allylic alkylation and amination reactions. Alkylation with dimethyl sodiomalonate produced only a small variation in the ee (89.3% to 93.4%), but amination with benzylamine gave a much wider variation in the ee (16.4% to 66.6%). Hammett analysis suggests that the substituents interact more significantly with phosphorus and supports a combined electronic and steric basis for enantioselection. [reaction: see text] 相似文献
15.
The heterocumulenes carbon dioxide (CO(2)), carbonyl sulfide (OCS), and carbon disulfide (CS(2)) were treated with bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin {[(CH(2))Me(2)Si](2)N}(2)Sn, an analogue of the well-studied bis[bis(trimethylsilyl)amido]tin species [(Me(3)Si)(2)N](2)Sn, to yield an unexpectedly diverse product slate. Reaction of {[(CH(2))Me(2)Si](2)N}(2)Sn with CO(2) resulted in the formation of 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane, along with Sn(4)(μ(4)-O){μ(2)-O(2)CN[SiMe(2)(CH(2))(2)]}(4)(μ(2)-N═C═O)(2) as the primary organometallic Sn-containing product. The reaction of {[(CH(2))Me(2)Si](2)N}(2)Sn with CS(2) led to formal reduction of CS(2) to [CS(2)](2-), yielding [{[(CH(2))Me(2)Si](2)N}(2)Sn](2)CS(2){[(CH(2))Me(2)Si](2)N}(2)Sn, in which the [CS(2)](2-) is coordinated through C and S to two tin centers. The product [{[(CH(2))Me(2)Si](2)N}(2)Sn](2)CS(2){[(CH(2))Me(2)Si](2)N}(2)Sn also contains a novel 4-membered Sn-Sn-C-S ring, and exhibits a further bonding interaction through sulfur to a third Sn atom. Reaction of OCS with {[(CH(2))Me(2)Si](2)N}(2)Sn resulted in an insoluble polymeric material. In a comparison reaction, [(Me(3)Si)(2)N](2)Sn was treated with OCS to yield Sn(4)(μ(4)-O)(μ(2)-OSiMe(3))(5)(η(1)-N═C═S). A combination of NMR and IR spectroscopy, mass spectrometry, and single crystal X-ray diffraction were used to characterize the products of each reaction. The oxygen atoms in the final products come from the facile cleavage of either CO(2) or OCS, depending on the reacting carbon dichalogenide. 相似文献
16.
An acoustic pointing task was used to measure extents of laterality produced by ongoing interaural temporal disparities (ITDs) conveyed by the envelopes of 4-kHz-centered raised-sine stimuli while varying, parametrically, their peakedness, depth of modulation, and frequency of modulation. One purpose of the study was to determine whether such manipulations would produce changes in laterality logically consistent with those found for ITD-discrimination thresholds reported by Bernstein and Trahiotis [J. Acoust. Soc. Am. 125, 3234-3242 (2009)]. The data obtained revealed that they did in that (1) increasing depth of modulation, peakedness, or frequency of modulation between 32 and 128 Hz produced smaller threshold ITDs and greater laterality and (2) increasing frequency of modulation to 256 Hz produced modest increases in threshold ITDs and modest decreases in laterality. The extents of laterality measured were successfully accounted for via an augmentation of the cross-correlation-based "position-variable" modeling approach developed by Stern and Shear [J. Acoust. Soc. Am. 100, 2278-2288 (1996)] to account for ITD-based extents of laterality obtained at low spectral frequencies. 相似文献
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We report on the interaction of alkyl-halide clusters with 35 ps and 20 fs laser pulses at λ = 266, 532, and 1064 nm and 400 and 800 nm, respectively. Particularly, we examine by means of time-of-flight mass spectrometry the intracluster photochemical processes, which give rise to the formation of molecular halogen ions. The efficiency of molecular halogen ion formation is found to depend strongly on the laser wavelength and pulse duration. The ionization/excitation schemes involve in both cases the multiphoton absorption by the clusters and the combined action of the laser and the intracluster electric field. Intracluster energy transfer processes seem to have a significant contribution to the molecular halogen ion formation in the ps domain, while in the fs region, this is probably facilitated by a rescattering process and/or by photon absorption. A physical mechanism for the interpretation of our experimental results is proposed. 相似文献
19.
Constantine A. Kagarakis 《Molecular physics》2013,111(6):1485-1488
The spectrum of a partially oriented sample of ethanol has been analysed by making use of the simpler spectra obtained from the species CD3CH2OH and CH3CD2OH, together with 1H?{2H} double resonance. With p-ethoxy-benzylidene-p-n-butylaniline (EBBA) as the nematic solvent the dipolar couplings of CH3 and CH2 protons with the OH proton can be observed, and their magnitudes are compared with values calculated assuming different models for C-O-H internal rotation. Information on the quadrupole coupling constant tensor elements for CD3 and CD2 deuterium nuclei is obtained. 相似文献
20.
This paper presents a perturbation theory for the double sine-Gordon equation. We obtain a system of differential equations that shows the soliton parameters modification under the influence of the perturbation. For the particular case λ=0 the results transform into the well-known perturbation theory for the sine-Gordon equation. 相似文献