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The crystallochemistry of and the bonding in the orthorhombic four-connected nets of BaIn(2) (CeCu(2) structure) and of CaPtSn (TiNiSi structure, a derivative of the CeCu(2) structure) are analyzed with approximate molecular orbital calculations. Following the Zintl concept, in BaIn(2) the In(-) ions are isoelectronic with group IV tin and should adopt a four-connected structure. In contrast to alpha-tin, which has a cubic diamond structure, the indium ions in BaIn(2) build up an orthorhombic three-dimensional four-connected net containing distorted tetrahedra and ladder polymers of four-membered rings. In the CeCu(2) structure (space group Imma) two bond angles in these distorted tetrahedra are fixed at 90 degrees. The four-connected net in the CeCu(2) structure is topologically related to the layers in black phosphorus (space group Cmca). In CaPtSn (TiNiSi structure) the orthorhombic four-connected net is formed by (PtSn)(2)(-) ions in an ordered arrangement. Calculations on BaIn(2) and CaPtSn show that the four-connected nets are increasingly stabilized as the valence electron count is increased from 16 to 30 valence electrons per 4 formula units. For more than 30e, the nets are destabilized due to filling of M-E antibonding states. Structural data obtained by precise single crystal investigations for the TiNiSi series CaPdIn (20e), CaPdSn (24e), CaPdSb (28e), and CaAgSb (32e), confirm the results of the extended Hückel calculations. We find an interesting and understandable angular asymmetry of the tetrahedral sites in these ternary compounds. 相似文献
84.
Yong‐Qian Wu David C. Limburg Douglas E. Wilkinson Gregory S. Hamilton 《Journal of heterocyclic chemistry》2003,40(1):191-193
A mild and efficient synthesis of five‐ and six‐membered nitrogen containing heterocyclic compounds, in which di(imidazole‐1‐yl)methanimine serves as a one‐carbon source, is reported. 相似文献
85.
[reaction: see text] Asymmetric aldol addition reactions have been conducted with (1R,2S)-ephedrine-derived 3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one (2). Diastereoselectivities range from 75:25 to 99:1 for the formation of the crude non-Evans syn adducts 8a-h. The facial selectivity of the enolate is directed by the stereogenic N(4)-methyl substituent. Aldol adduct 8a is readily cleaved by acid hydrolysis to afford (2S,3S)-3-hydroxy-2-methyl-3-phenylpropionic acid (9) in >95% ee. 相似文献
86.
The addition of 4.0 equiv of Na(silox) to Na[W(2)Cl(7)(THF)(5)] afforded (silox)(2)ClW&tbd1;WCl(silox)(2) (1, 65%). Treatment of 1 with 2.0 equiv of MeMgBr in Et(2)O provided (silox)(2)MeW&tbd1;WMe(silox)(2) (2, 81%). In the presence of 1 atm of H(2), reduction of 1 with 2.0 equiv of Na/Hg in DME provided (silox)(2)HW&tbd1;WH(silox)(2) (3, 70%), characterized by a hydride resonance at delta 19.69 (J(WH) = 325 Hz, (1)H NMR). Exposure of 2 to 1 atm of H(2) yielded 3 and CH(4) via (silox)(2)HW&tbd1;WMe(silox)(2) (4); use of D(2) led to [(silox)(2)WD](2) (3-d(2)). Exposure of 3 to ethylene ( approximately 1 atm, 25 degrees C) in hexanes generated (silox)(2)EtW&tbd1;WEt(silox)(2) (5), but solutions of 5 reverted to 3 and free C(2)H(4) upon standing. NMR spectral data are consistent with a sterically locked, gauche, C(2) symmetry for 1-5. Thermolysis of 3 at 100 degrees C (4 h) resulted in partial conversion to (silox)(2)HW&tbd1;W(OSi(t)Bu(2)CMe(2)CH(2))(silox) (6a, approximately 60%) and free H(2), while extended thermolysis with degassing (5 d, 70 degrees C) produced a second cyclometalated rotational isomer, 6b (6a:6b approximately 3:1). When left at 25 degrees C (4 h) in sealed NMR tubes, 6 and free H(2) regenerated 3. Reduction of 1 with 2.0 equiv of Na/Hg in DME also afforded 6a (25%). When 3 was exposed to approximately 3 atm of H(2), equilibrium amounts of [(silox)(2)WH(2)](2) (7) were observed by (1)H NMR spectroscopy (3 + H(2) right harpoon over left harpoon 7; 25.9-88.7 degrees C, DeltaH = -9.6(4) kcal/mol, DeltaS = -21(2) eu). Benzene solutions of 3 and 1-3 atm of D(2) revealed incorporation of deuterium into the silox ligands, presumably via intermediate 6. In sealed tubes containing [(silox)(2)WCl](2) (1) and dihydrogen (1-3 atm), (1)H NMR spectral evidence for [(silox)(2)WCl](2)(&mgr;-H)(2) (8) was obtained, suggesting that formation of 3 from 1 proceeded via reduction of 8. Alternatively, 3 may be formed from direct reduction of 1 to give [(silox)(2)W](2) (9), followed by H(2) addition. Hydride chemical shifts for 7 are temperature dependent, varying from delta 1.39 (-70 degrees C, toluene-d(8)), to delta 3.68 (90 degrees C). (29)Si{(1)H} NMR spectra revealed a similar temperature dependence of the silox (delta 12.43, -60 degrees C, to delta 13.64, 45 degrees C) resonances. These effects may arise from thermal population of a low-lying, deltadelta, paramagnetic excited state of D(2)(d)() [(silox)(2)W](2)(&mgr;-H)(4) (DeltaE approximately 2.1 kcal/mol, chi(7a) approximately 0.03), an explanation favored over thermal equilibration with an energetically similar but structurally distinct isomer (e.g., [(silox)(2)WH(2)](2)(&mgr;-H)(2), DeltaG degrees approximately 0.69 kcal/mol, chi(7b) approximately 0.25) on the basis of spectral arguments. Extended Hückel and ab initio molecular orbital calculations on model complexes [(H(3)SiO)(2)W](2)(&mgr;-H)(4) (staggered bridged 7a', EHMO), [(H(3)SiO)(2)WH(2)](2) (all-terminal 7b', EHMO), [(H(3)SiO)(2)W](2) (9', EHMO), (HO)(4)W(2)(H(4)) (staggered-bridged 7", ab initio), and (HO)(4)W(2)(H(4)) (bent-terminal 7, ab initio) generally support the explanation of a thermally accessible excited state and assign 7 a geometry intermediate between the all-terminal and staggered-bridged forms. 相似文献
87.
88.
Barnes JH Schilling GD Stone SF Sperline RP Denton MB Young ET Barinaga CJ Koppenaal DW Hieftje GM 《Analytical and bioanalytical chemistry》2004,380(2):227-234
The use of a separation step, such as liquid chromatography, prior to inductively coupled plasma mass spectrometry (ICP–MS) has become a common tool for highly selective and sensitive analyses. This type of coupling has several benefits including the ability to perform speciation analysis or to remove isobaric interferences. Several limitations of conventional instruments result from the necessity to scan or pulse the mass spectrometer to obtain a complete mass spectrum. When the instrument is operated in such a non-continuous manner, duty cycle is reduced, resulting in poorer absolute limits of detection. Additionally, with scanning instruments, spectral skew can be introduced into the measurement, limiting quantitation accuracy. To address these shortcomings, a high-performance liquid chromatograph has been coupled to an ICP–MS capable of continuous sample introduction and simultaneous multimass detection. These features have been realized with a novel detector array, the focal plane camera. Instrument performance has been tested for both speciation analysis and for the elimination of isobaric interferences. Absolute limits of detection in the sub picogram to tens of picograms regime are obtainable, while the added mass dimension introduced by simultaneous detection dramatically increases chromatographic peak capacity. 相似文献
89.
Three-dimensional (3-D) structures with micron-sized features have been fabricated via the direct-write assembly of polyelectrolyte inks. By mixing oppositely charged species under solution conditions that promote polyelectrolyte exchange reactions, we have created concentrated fluids capable of flowing through microscale deposition nozzles. Ink deposition into an alcohol/water coagulation reservoir yielded polyelectrolyte filaments that rapidly solidify to enable three-dimensional patterning of microperiodic structures with self-supporting features. The influence of ink and reservoir chemistry on the phase behavior, rheological properties, and assembly of concentrated polyelectrolyte complexes is reported with an emphasis on the optimal conditions for 3-D writing. 相似文献
90.
Self-assembly of nonionic surfactants into lyotropic liquid crystals in ethylammonium nitrate, a room-temperature ionic liquid 总被引:2,自引:0,他引:2
The stability of a variety of lyotropic liquid crystals formed by a number of polyoxyethylene nonionic surfactants in the room-temperature ionic liquid ethylammonium nitrate (EAN) is surveyed and reported. The pattern of self-assembly behaviour and mesophase formation is strikingly similar to that observed in water, even including the existence of a lower consolute boundary or cloud point. The only quantitative difference from water is that longer alkyl chains are necessary to drive the formation of liquid crystalline mesophases in EAN, suggesting that a rich pattern of "solvophobic" self-assembly should exist in this solvent. 相似文献