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71.
Fu Qiang Huang 《Journal of solid state chemistry》2003,174(2):334-341
Three new compounds, Cs2Bi2ZnS5, Cs2Bi2CdS5, and Cs2Bi2MnS5, have been synthesized from the respective elements and a reactive flux Cs2S3 at 973 K. The compounds are isostructural and crystallize in a new structure type in space group Pnma of the orthorhombic system with four formula units in cells of dimensions at 153 K of a=15.763(3), b=4.0965(9), c=18.197(4) Å, V=1175.0(4) Å3 for Cs2Bi2ZnS5; a=15.817(2), b=4.1782(6), c=18.473(3) Å, V=1220.8(3) Å3 for Cs2Bi2CdS5; and a=15.830(2), b=4.1515(5), c=18.372(2) Å, V=1207.4(2) Å3 for Cs2Bi2MnS5. The structure is composed of two-dimensional ∞2[Bi2MS52−] (M=Zn, Cd, Mn) layers that stack perpendicular to the [100] axis and are separated by Cs+ cations. The layers consist of edge-sharing ∞1[Bi2S66−] and ∞1[MS34−] chains built from BiS6 octahedral and MS4 tetrahedral units. Two crystallographically unique Cs atoms are coordinated to S atoms in octahedral and monocapped trigonal prismatic environments. The structure of Cs2Bi2MS5, is related to that of Na2ZrCu2S4 and those of the AMM′Q3 materials (A=alkali metal, M=rare-earth or Group 4 element, M′= Group 11 or 12 element, Q=chalcogen). First-principles theoretical calculations indicate that Cs2Bi2ZnS5 and Cs2Bi2CdS5 are semiconductors with indirect band gaps of 1.85 and 1.75 eV, respectively. The experimental band gap for Cs2Bi2CdS5 is ≈1.7 eV, as derived from its optical absorption spectrum. 相似文献
72.
We herein report on solution structural studies of Ru^Ⅱ catalysts (3a, 9) composed of achiral bisphosphine ligands (4, 8) and the enantiopure 1,2-diphenylethylenediamine (DPEN). Complete chiral induction from enantiopure (R,R)-DPEN to achiral bisphosphine ligand 3a was observed in solution, with the complex adopting a single, stable and non-fluxional (even at 70 ℃) configuration. The coordination of the C=O moiety in 4 to the cationic Run center is considered to be of key importance in providing the higher thermodynamic and kinetic rotation barrier for the flexible bisphosphine ligand in the complex. The obtained enantioselectivity (91% enantiomeric excess) and sense of chiral induction in the hydrogenation of acetophenone were found to be solely dependent on the chirality of the 1,2-diamine. Consistent with the hydrogenation product, the (R,R)-DPEN induces a M-conformation (fight-handed) chirality for flexible phosphine ligand 4 in the complex, resulting in a 2,2-configuration about the Ru^Ⅱ center. 相似文献
73.
Shimpei Sugiyama 《Tetrahedron letters》2005,46(39):6771-6775
Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from symmetrical ketones and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with lithium enolate of carboxylic acid tert-butyl esters gave optically active adducts having a substituent at the α-position with high 1,4-chiral induction from the sulfur chiral center in high yields. The adducts were converted to optically active esters and carboxylic acids having a chiral center at the α-position. When this addition reaction was carried out with the ester enolate generated from excess carboxylic acid tert-butyl ester with LDA in the presence of HMPA, the diastereomer of the adduct was obtained. By using the two reaction conditions for the generation of the ester enolates, a new method for asymmetric synthesis of both enantiomers of carboxylic acid derivatives having a substituent at the α-position from the one chiral source, (R)-(−)-chloromethyl p-tolyl sulfoxide, was realized. 相似文献
74.
The influence of Stokes shift in optosensing was discussed. Then, the current status of large Stokes shift-based optosensing was reviewed here. 相似文献
75.
Laser Doppler anemometry is used for the measurements of the plasma and particle velocity profiles in the coil region of an inductively coupled r.f. plasma. Results are reported for a 50 mm i.d. induction plasma torch operated at atmospheric pressure with argon as the plasma gas. The oscillator frequency is 3 MHz and the plate power is varied between 4.6 and 10.5 kW. Plasma velocity measurements are obtained using a fine carbon powder as a tracer. Measurements are also given for larger silicon particles (
) centrally injected into the discharge under different operating conditions.Nomenclature
d
p
particle diameter
-
P
0
plasma power
-
Q
1
powder carrier gas flow rate
-
Q
2
plasma gas flow rate
-
Q
3
sheath gas flow rate
-
r
distance in the radial direction
-
V
axial plasma velocity
-
V
p
axial particle velocity
-
Z
distance in the axial direction
-
standard deviation 相似文献
76.
In on-column or in splitless injection with recondensation of the solvent, the length of the flooded zone in the column inlet depends primarily on the wettability of the internal wall of the inlet. For columns with a coated inlet this explains why peak distortion due to band broadening in space by a certain sample volume is pronounced in one case and hardly observable in another. Glass or fused silica capillaries silylated with diphenyltetramethyldisilazane were found to give optimal retention gaps. They combine thorough and thermostable deactivation with good wettability and low retention power. On the other hand it is very easy to deactivate fused silica capillaries with Carbowax. The resulting retention gaps are suitable for a wide range of applications and are particularly attractive for the analysis of dirty samples which require frequent replacement of the inlet. 相似文献
77.
采用B3LYP/6-31G*方法,对内含式化合物X@B12P12(X=Li0/+、Na0/+、K0/+、Be0/2+、Mg0/2+、Ca0/2+、H和He)的不同对称性构型进行了计算,讨论其最稳定构型的几何参数、布居分析、偶极矩、电离势、包含能、振动频率、能隙和自旋密度. 发现在X@B12P12化合物中,客体X=Li、Na0/+、K0/+、Mg0/2+、Ca0/2+和He处在偏离笼的中心0.006 nm的半径内. Be2+沿着C3轴偏离中心点0.279 nm. 在Be@B12P12和H@B12P12的基态结构中,Be和H与笼上的B原子成键. 除Li@B12P12、 Be2+@B12P12和He@ B12P12外, 其余结构为Cs对称稳定构型. 相似文献
78.
The dipole moments of a number of substituted benzaldehydes are measured in benzene solution. The angle which the dipole axis
of the CHO group makes with the axis of rotation of the group is determined. The observed moments of the ortho-substituted
benzaldehydes are compared with the moments calculated for free rotation as well as fors-trans ands-cis orientations of the -CHO group.o-Fluorobenzaldehyde exists mostly in thes-trans conformation.o-Chloro-,o-bromo-ando-nitro-benzaldehydcs also exist in thes-trans conformation; their observed dipole moments are even lower than the values calculated fors-trans forms, indicating mutual induction of the ortho substituents. Though 2,5-dichlorobenzaldehyde is expected to have the same
dipole moment as benzaldehyde, the observed moment is significantly lower due to mutual induction of the ortho substituents.
2,5-Dimethylbcnzaldehyde has, however, almost the same moment as benzaldehyde. The dipole moment ofo-methoxybcnzaldchyde is considerably higher than the values calculated for boths-cis ands-trans conformations. An explanation is given for this.o-Hydroxybenzaldehyde exists exclusively in thes-cis form due to internal H-bonding. 相似文献
79.
手性胶束的不对称诱导作用不对称苯偶姻缩合反应 总被引:2,自引:0,他引:2
胶束体系是模拟酶的简单模型之一。手性胶束对反应有手性诱导作用。在表面活性剂(1R,2S)-(-)-N-十二烷基-N-甲基麻黄素溴化物和(1R,2S)-(-)-N-十六烷基-N-甲基麻黄素溴化物形成的胶束体系中进行的苯偶姻缩合反应,生成了光学活性的α-羟基酮。 相似文献
80.
Hidetaka KogaEiji Wada 《Tetrahedron letters》2003,44(4):715-719
An efficient catalytic double asymmetric induction during the tandem transetherification-intramolecular hetero Diels-Alder reaction has been developed. The enantioselective tandem reaction of methyl (E)-4-methoxy-2-oxo-3-butenoate with rac-6-methyl-5-hepten-2-ol has been achieved to provide methyl (2R,4aS,8aR)-3,4,4a,8a-tetrahydro-2,5,5-trimethyl-2H,5H-pyrano[4,3-b]-pyran-7-carboxylate in good yield with effective kinetic resolution (up to 95% selectivity), high diastereoselectivity (up to 92% de), and high enantioselectivity (up to 97% ee) in the presence of (S,S)-tert-Bu-bis(oxazoline)-Cu(SbF6)2 and 5 Å molecular sieves. 相似文献