Calculation and analysis of the frequencies of normal vibrations of 2,3-Di-O-nitro-methyl-β-D-glucopyranoside

A calculation of the frequencies and forms of the normal vibrations of the 31-atom molecule 2,3-di-O-nitromethyl-β-D-glucopyranoside has been performed. Particular emphasis has been placed on the interpretation of the strongest bands in the spectrum of 2,3-di-O-nitro-methyl-β-D-glucopyranoside, which are due to vibrations of the nitrate groups. The present work has been reported at the IV International Congress of theoretically competent chemists, Jerusalem (Israel), July 7–12, 1996. B. I. Stepanov Institute of Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 724–728, November–December, 1997.     

1,8-萘啶氮氧化物与碱土金属硝酸盐的荧光固态配合物的合成及性质

以1,8-萘啶氮氧化物为配体的金属寓子配合物尚未见文献报道,继1,8-萘啶氮氧化物与镧系金属离子的配合物合成之后,我们又合成了1,8-萘啶氮氧化物与碱土金属硝酸盐的荧光固态配合物,并对其性质进行亍研究。     

新氮杂冠醚衍生物稀土硝酸盐配合物的制备、表征及荧光性质

通过N3O2大环化合物1，12，15-三氮杂-3，4：9，10-二苯-5，8-二氧杂环十七烷(以下简称为L)与乙酸酐、苯甲酰氯、邻苯二甲酸酐在吡啶介质中反应，合成了N，N’，N”-三乙酰(L^1)、N，N’，N”-三(2-羧基)苯甲酰(L2)、N，N’，N”-三苯甲酰(L3)N3O2大环配体，并制备了L^1的Sm，Eu，Tb，Dy稀土硝酸盐的配合物。通过元素分析、摩尔电导、热分析、红外的测定对配合物进行了表征。结果表明，L^1母体环上的醚氧、酰胺氮均没有参与对稀土离子的配位，并推测了配合物的可能组成。室温下研究了配合物的固体荧光光谱，固态时的配合物(除Sm^3 配合物外)均有较强荧光，其中Tb^3 配合物的荧光强度最高，表明配体三重态的能量与Tb^3 的振动能级更为匹配。在Eu^3 的配合物中，强度比η(^5Do→^7F2/Do→^7F1)=3．7，表明Eu^3 处于一非对称配位环境中。     

The role of anhydrous zinc nitrate in the thermal decomposition of the zinc hydroxy nitrates Zn5(OH)8(NO3)2·2H2O and ZnOHNO3·H2O

The steps associated with the thermal decomposition of Zn₅(OH)₈(NO₃)₂·2H₂O and ZnOHNO₃·H₂O are re-examined. Previous reports have suggested that Zn₅(OH)₈(NO₃)₂·2H₂O decomposes to ZnO via two intermediates, Zn₅(OH)₈(NO₃)₂ and Zn₃(OH)₄(NO₃)₂ whereas ZnOHNO₃·H₂O has been reported to decompose to ZnO via a Zn₃(OH)₄(NO₃)₂ intermediate. In this study, we demonstrate using TG, mass spectral analysis of evolved gases and in situ variable temperature powder X-ray diffraction analysis that, in fact, in the decomposition of Zn₅(OH)₈(NO₃)₂·2H₂O an anhydrous zinc nitrate intermediate is also involved. We, additionally, show that the decomposition of ZnOHNO₃·H₂O to ZnO also involves the formation of an anhydrous zinc nitrate intermediate. The anhydrous zinc nitrate formed in both cases is poorly crystallised and this observation may explain why this phase could not be observed by PXRD analysis in the previous studies.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Structure of solvated metal ions in nitrate and chloride solutions of erbium(III) and yttrium(III) in dimethyl sulfoxide

X-ray diffraction measurements on 1M yttrium(III) and erbium(III) nitrate and chloride solutions in dimethyl sulfoxide (DMSO) have shown that Er(III) and Y(III) solutions of equal compositions are isostructural. The intensity difference functions can then be used to derive the detailed structure of the coordination sphere around the metal ions. The DMSO molecules are coordinated over oxygen with average M-O-S bond angles of about 130°. Two different conformations, corresponding to different relative orientations of the M-O and O-S bonds, seem to be prevalent. In the nitrate solutions an average of about 1.5 nitrate ions are coordinated as bidentate ligands to each metal ion. In the chloride solutions about 1.3 chloride ions belong to the inner-coordination sphere.On leave from the Department of Inorganic Chemistry, Royal Institute of Technology, S-10044 Stockholm, Sweden     

Abtrennung von Ceriterden aus Gemischen mit Yttererden durch fraktionierte Kristallisation der Magnesiumdoppelnitrate in großem Maßstab

Summary The fractional crystallisation of magnesium double nitrates was used to separate cerium earths from 112 kg yttrium earth mixtures; they were recovered in three different fractions. By using excess magnesium nitrate the crystallisation could be extended at least to gadolinium without using HNO₃ as solvent. In the resulting solutions (69 kg oxide) there remained yttrium and nearly all erbium and heavy yttrium earths.

     

固体酸催化剂和载体上芳烃的选择性硝化

硝化研究的重要意义之一是探索更具选择性的方法。该文讨论了应用同体酸催化剂和载体，在醋酐存在下，采用硝酸盐和载体硝酸盐硝化甲苯和氯苯的选择性．8种金属硝酸盐中，硝酸铜表现好的硝化特性。层状粘士较沸石分子筛、杂多酸盐等是颇具前景的芳烃选择性硝化催化剂和载体．四氯化碳和甲苯为较好的溶剂介质．阻此条件，甲苯和氯苯的划邻硝化产物比例分为1.2和5.6，较之硝硫混酸的结果（甲苯0.6，氯苯1.8）．其对位硝化能力显著提高。     

金属硝酸盐—醋酐硝化反应机理研究

利用竞争硝化法可以求得一系列单取代苯相对于苯的反应活性,据此就能建立金属硝酸盐—醋酐硝化反应的Hammett方程,求得该反应的反应常数ρ=-6.24。该值与文献报导的其它硝化剂硝化反应所得到的值相近,从而认为该条件下的活化硝化剂仍是NO_2~+,其历程为电荷控制反应。将金属硝酸盐吸附在载体上进行反应可以得到较好的位置选择性,这主要是由于载体及该反应体系低的介电常数的作用。     

稀土硝酸盐与L—α亮氨酸固体配合物的合成与表征

在无水乙醇和苯的混合溶剂中,制得了稀土硝酸盐和L—a亮氨酸的6种固体配合物.经化学分析、元素分析和热重分析确定了其组成是RE(Leu)_3(NO_3)_3H_2O(RE=Pr,Nd,Sm,Eu,Gd)和Dy(Leu)_4(NO_3)_3·H_2O(Leu=Leucine亮氨酸);测定了熔点,并通过TG—DTG比较了它们的热稳定性.