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71.
72.
d~9电子构型的金属离子所形成的配合物几何构型一般为拉长八面体或平面正方形,晶体场理论和角重叠模型都对此作出了较满意的描述,但就该电子构型的中心离子与指定配体配位时易形成配合物的配位数、配体所处的位置等问题,至今尚无满意解释.本文通过分子轨道稳定化能(MOSE)的计算及其曲面的绘制,形象地解释了上述问题. 相似文献
73.
Ashok K. Ganguli Shalabh Gupta Jing-Tae Zhao E. Alejandro Leon-Escamilla 《Journal of solid state chemistry》2005,178(10):2959-2972
A particular pathology of certain W5Si3-type A5B3 structures (I4/mcm) appears to arise because of unduly close approaches of the A1-type atoms on the cell faces at , 0, () that occur with the larger and more electropositive A and/or in the presence of smaller B atoms. A structure refinement of binary Ba4.81Pb3 indicates such a marginal stability in that the Ba atoms in the facial Ba0.81 chains exhibit an extreme displacement ellipsoid along . Although Ca5Sn3 and La5Ga3 binaries are unknown in this structure type, five stable ternary derivatives of these have been synthesized via substitution reactions and characterized by single crystal X-ray diffraction means: Ca4Sn3.223(4)Mg0.777, Ca4Sn3Cu1.30(4), Ca4.66(6)Sn3Zn0.704(4), La4.81(1)Ga1.38(2)Al1.62, and La4.762(5)Ga1.5(1)Zn1.5. Only the Ca-Sn-Zn phase exhibits lower symmetry, P4/mbm. The problematic A1 sites exhibit diverse changes in these, whereas the surrounding B2 tetrahedra are largely unaltered. The Ca-Sn results are, respectively: direct Mg/Sn substitution at the Ca1 site; mixed fractional distribution of the smaller Cu at two sites around the A1 position with an unresolved disorder; a pair of apparently independent modes, fractional Ca in the normal position and fractional Zn rectangles thereabout. The two La-Sn phases contain normal Ga,Al (Ga,Zn) tetrahedral chains with pairs of fractional disordered La atoms along , 0, z. Each can be rationalized in terms of a reasonable incommensurate structure. Electronic effects may also be operable. 相似文献
74.
X. Bokhimi A. Morales E. Ortíz T. López R. Gómez J. Navarrete 《Journal of Sol-Gel Science and Technology》2004,29(1):31-40
Sol-gel titania was sulfated by using sulfuric acid as hydrolysis catalyst, or by impregnating with ammonium sulfate fresh samples prepared with nitric acid or ammonium hydroxide as hydrolysis catalyst. Samples were characterized with X-ray powder diffraction, infrared spectroscopy, thermogravimetry and atomic absorption spectroscopy. Sulfate ions were found anchored to brookite and anatase phases, because they have short O—O atomic bond lengths slightly larger than the largest O—O bond length of sulfate ion. Since the shortest O—O atomic bond in anatase is smaller than the one in brookite, the sulfate ions are then less deformed when they are anchored to anatase, and consequently more stable. Therefore when the sample temperature is raised, the brookite with sulfate ions was transformed mainly to anatase and not into rutile, which is the most probably transformation when these ions are not involved. Sulfate ions also hindered anatase and brookite crystallite growing and stabilized the crystalline structure of anatase. When the sulfate ions are lost the crystalline anatase phase is transformed into rutile, leaving a large number of vacancies that favored atom diffusion and consequently the growing of rutile crystallites. The crystalline evolution of the samples as a function of the annealing temperature is almost independent of the sulfating method. 相似文献
75.
The most stable structure of CB2H3
–, as established computationally, is the aromatic diboracyclopropenyl (diboriranyl) anion (5), while open-chainC
2v, isomer H2BCBH (7) is only 3 kcal/mol higher in energy at the QCISD(T)/6-311 +G**//MP2/6-31+G*+ZPE (HF/6-31 +G*). The 47-kcal/mol barrier between cyclic,5, and open-chain,7, structures suggests that both of them may be observed. The aromatic stabilization energy of the diboriranyl anion (18 kcal/mol) is half the value in the isoelectronic cyclopropenium ion, C3H3
+. The computed, by IGLO method (5a), and experimental (6a) chemical shifts,(13C) and(11B), agree within 4 ppm range. The theoretical vibrational frequencies of the most stable isomers,5 and7, are presented for experimental verification of these species. 相似文献
76.
The effect of pH on the dilution enthalpies of D-p-hydroxyphenylglycine in phosphate buffer solutions has been investigated by isothermal titration microcalorimetry at 298.15 K. The corresponding homogeneous enthalpic interaction coefficients have been calculated according to the excess enthalpy concept. The results show that the enthalpies of dilution of D-p-hydroxyphenylglycine in phosphate buffer solutions at different pH are all positive. The overall trend is that enthalpies of dilution become more positive with an increase of pH, but there is a minimum of the enthalpy of dilution at pH = 7.0. The enthalpic pair interaction coefficients, h
2, all have negative values. The results are interpreted from the point of view of solute-solute and solute-solvent interactions involved in the solvent effects. 相似文献
77.
2,2'-二乙炔基-1,1'-联萘为模板构筑的新的环芳化合物的合成及其光学性质 总被引:1,自引:0,他引:1
基于2,2'-二取代的联萘衍生物在手性构型上高度稳定的特点,分别以光学活性的(R)-和(S)-2,2'-二乙炔基-1,1'-联萘为模板,设计了2个有趣的拓扑环芳分子四联萘笼状对映异构体(R,R,R,R)-2和(S,S,S,S)-2.其合成路线涉及保护基的控制导入、苯连接桥的链接、保护基的脱去以及偶合成环反应4个步骤.用MS,IR,UV-Vis,1HNMR,13CNMR和元素分析等技术对其进行了表征,并比较了其光学性质.研究结果表明,采用这种模板合成方法能够有效地获得具有单一手性的目标化合物.镜像特征的圆二色(CD)谱和比旋光度[α]D的测定结果清楚地反映了它们的对映异构关系. 相似文献
78.
本工作采用溴加成法、酚解法、FTIR法及臭氧裂解法分别测定了五种不饱和蒸气压下聚合的PVC样品(u-PVC)和五种商品PVC样品(s-PVC)的总双键、总不稳定氯、孤立双键和内部双键的含量.通过研究结构缺陷和PVC的平均分子量及脱HCl速率的相互关系,揭示了不饱和总双键值,总不稳定氯和孤立双键含量彼此的相关性是建立在它们分别与1/M_n的相关性基础之上,从而得出了这三种定量值测得的主要都是端基烯丙基氯结构.根据三者对脱HCl速率的良好线性相关性,首次提出了端基烯丙基氯结构在HCl催化作用下异构化成内部烯丙基氯从而成为脱HCl速率主要原因的机理. 相似文献
79.
BAO Ren-lie KONG Zu-ping GU Min YUE Bin WENG Lin-hong HE He-yong 《高等学校化学研究》2006,22(6):679-683
IntroductionSynthesis of natural minerals is helpful for tracingthe geological origin of mineral formation and forverifying the quality of minerals. The investigations onthe conditions for mineral formation, such as pressure,temperature, and starting mate… 相似文献
80.
用MNDO方法,全构型优化,研究了15个氮自由基4-RC6H4NH,和15个氧自由基4-RC6H4O(R=-H;-OCH3,-Cl,-F,-CN,-COCH3,-NO2,-CH3,-CF3,-SCH3,-C6H5,-Nh2,-BH2,-PH2,-SiH3)的稳定化能.结果表明:-NH2,-CH3,-OCH3,-F基团对自由基起稳定化作用,-CF3,-NO2;-CN,-COCH3,-BH2基团对自由基起去稳定化作用.苯基对氧自由基有较大的稳定化作用,而对氮自由基的稳定性影响较小.-SCH3,-PH2,-SiH3,-Cl基团表现弱的去稳定化作用.计算和实验结果基本相符. 相似文献