叠氮二异丁基铝的构造及其缔合-解离平衡研究

叠氮二异丁基铝（DBAA）是一个新合成的化合物。通过相对分子质量的测定、氢－核磁共振谱和铝－核磁共振谱的测定,确定了DBAA三聚体的分子构造;在溶液中研究了DBAA的三聚体和单晶体之间的缔合－解离平衡。这个平衡受溶剂性质、温度的影响。借助铝－核磁共振谱和相对分子质量的测定计算了DBAA三聚体的解离平衡常数、解离焓和解离熵等热力学数据。     

叠氮二乙基铝合成及其相关反应的研究

在芳烃溶剂中用氯化二乙基铝和叠氮化钠反应合成了叠氮化二乙基铝(DEAA),其产率高达87%,比文献值高出17%。在正己烷中没有合成出DEAA,在含30%四氢呋喃(THF)的正己烷中合成出DEAA·THF配合物。在芳烃溶剂中,随着苯环上甲基数目的增加,DEAA的收率增加。测定了氯化二乙基铝、氯化二乙基铝的正己烷溶液、氯化二乙基铝的甲苯溶液的 ²⁷Al NMR谱。由 ²⁷Al NMR谱数 据确定了氯化二乙基铝在甲苯中解离平衡式,计算了氯化二乙基铝在甲苯中解离平衡的热力学数据。用DEAA与苯甲酸甲酯直接合成了苯甲酰叠氮,并表征了其结构。这是一个新反应,至今无文献报导。用实验证明了在正己烷溶液中,用氯化二乙基铝、叠氮化钠与苯甲酸甲酯合成苯甲酰叠氮,没有经过氯化二乙基铝和叠氮化钠反应生成中间体DEAA的这一步。依据实验事实建立了上述三种反应的反应机理。     

1-烷基-4-氨基-1,2,4-三唑硝酸盐含能离子液体的蒸气压及其摩尔汽化焓的理论研究

合成了1-烷基-4-氨基-1,2,4-三唑硝酸盐含能离子液体([RATZ]NO₃),并通过核磁和红外进行了结构表征;采用Gaussian09/B3LYP/6-311+G(d,p)密度泛函理论,计算了[RATZ]NO₃的离子间相互作用能及摩尔体积;在298 K-323 K温度范围内,测定了不同配比[RATZ]NO₃-EtOH混合溶液的饱和蒸气压,其中乙醇摩尔分数分别为0.984、0.996、0.999以及1.000。系统研究了[RATZ]NO₃-EtOH混合溶液的饱和蒸气压、[RATZ]NO₃的蒸气压及摩尔汽化焓与温度、离子间相互作用能以及结构之间的关系。结果表明：[RATZ]NO₃-EtOH混合溶液的饱和蒸气压随着温度的升高、离子间作用能的减小以及阳离子体积的增大而增大,其沸点比纯溶剂高,且在298 K-323 K温度范围内[RATZ]NO₃的平衡蒸气压均低于250 mPa,因此说明含能离子液体具有不挥发性,蒸气压极低,并通过理论计算得到的离子间相互作用能及体积,解释了[RATZ]NO₃的摩尔汽化焓随烷基链增长而降低的原因。     

钇(Ⅲ)的二特戊酰基甲烷螯合物的合成、表征及热稳定性和升华性能研究

合成了钇(Ⅲ)的二特戊酰基甲烷螯合物(简称Y(DPM)₃)，并以红外光谱、核磁共振谱及X-射线物相分析进行了表征和鉴定。研究了这种β-二酮类螯合物的升华性能。结果表明，其升华速率与温度呈指数关系，与载气流量呈线性关系；通过测定蒸气压与温度之间的关系，求得130℃～164℃温度范围内的升华焓和升华熵，分别为135 kJ·mol^-1和265 J·mol^-1·K^-1。实验研究表明，该螯合物具有良好的挥发性和热稳     

低熔点晶体叠氮二乙基铝的合成和证明

叠氮二乙基铝（DEAA)是叠氮有机铝化合物中比较重要的一个化合物,但对DEAA的合成报道很少,还没有分离出纯的DEAA的报道。对它的研究有着重要的理论意义和应用价值。DEAA用作叠氮化试剂可用于多种叠氮化反应^[1-3];作为MOCVD前体物,由DEAA可制得性能优良的纳米级AIN材料,如AIN微晶薄膜^[4-6]和AIN粉末材料;DEAA是高含能材料,在国防和空间技术领域有着潜在的应用前景。文献报道的DEAA的合成方法按原料可分为三种^[7-10],其中以叠氮化钠和氯化二乙基铝（DEAC）为原料的合成方法应用较广,得到的DEAA为无色透明液体,熔点为－130℃^[11]。但笔者曾和到过固体DEAA^[12]。因此,本文将主要就DEAA的形态问题展开研究。     

碳氢燃料的蒸发焓与1H NMR结构参数

用500MHz超导核磁共振仪测定了36个碳氢燃料油的^1HNMR谱，获得各类氢的相对含量。假设碳氢燃料由直链烷烃和直链烷基苯两种模型化合物构成，^1HNMR结果和相对分子质量计算了相应的基团组成数。采用斜式沸点计测定燃料在不同温度下的泡点蒸气压，根据Clausius-Clapeyron方程计算了燃料的蒸发焓和蒸发熵。以基团贡献法为桥梁，把微观的^HNMR结构信息与宏观的蒸发性质联系起来，给出一个预测碳氢燃料蒸发焓的基团贡献表达式，检验结果表明偏差为 5.4％- -5.9％（平均2.1％）。用此表达式预测了17个纯烃和石油馏分的蒸发焓，偏差为 8.5％- -10.1％（平均3.3％）。     

铝离子对α-酮戊二酸的催化脱羧作用

为了研究铝(Ⅲ)与生命体中重要的有机分子α-酮戊二酸的作用机制,我们采用了电位滴定、核磁共振、拉曼光谱和分子力学计算对酸性溶液中的反应体系的配位作用和互变异构进行了分析, 并采用电喷雾质谱以及固体和溶液核磁共振谱表征了浓溶液反应体系中的沉淀,来说明铝(Ⅲ)对α-酮戊二酸的催化脱羧反应过程。得到如下实验结论:(1)配位作用:铝(Ⅲ)与α-酮戊二酸在酸性溶液中配位形成1∶1[AlLH²⁺,AlL⁺,AlLH_-1]和1∶2[AlL₂]-,AlL₂]H_-2]^3-]的单核形态以及2∶1[Al₂]L⁴⁺]的双核形态。(2)互变异构:在酸性溶液中Al³⁺通过配位作用促进α-酮戊二酸烯醇化,生成易于脱羧的β、γ-不饱和酸的结构。(3)催化脱羧:由于铝(Ⅲ)的电子沉降作用,使β、γ-不饱和酸更易脱羧,如果是1∶2的形态,则脱羧生成沉淀。     

缔合溶液热力学性质与谱学性质的关联

缔合溶液具有与理想溶液显著不同的热力学和谱学性质,对于热力学和谱学的研究,有助于我们理解缔合溶液的特殊行为.谱学技术中核磁共振(NMR)、红外(IR)和拉曼(Raman)光谱是研究分子间相互作用和溶液结构等微观性质的有效方法,谱学已成为分子热力学研究体系"四面体结构"中的第四个顶点.本文对缔合溶液中热力学(汽液平衡和焓)和谱学(NMR,IR和Raman)联系的最新研究进展进行了综述,着重介绍相关的模型,如化学缔合模型、局部组成(LC)、格子流体氢键(LFHB)理论以及统计缔合流体理论(SAFT).     

高浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用

利用红外和拉曼光谱技术研究了不同浓度LiClO₄/丙酮溶液中离子-溶剂和离子-离子的相互作用. 红外和拉曼光谱的分析表明, Li^＋与丙酮分子发生了强烈的相互作用, 导致丙酮C—C伸缩振动谱带、C＝O伸缩振动谱带等发生了分裂. Li^＋的溶剂化数随溶液浓度的增加逐渐降低, 在所研究的LiClO₄浓度范围(0.31～3.98 mol•kg^－1)内由3.4减小到1.9. 此外, 根据的谱带变化确定了溶液中存在的多种离子对的形式, 计算了缔合平衡常数, 并与电导实验结果进行了比较, 解释了这两种方法测定的离子缔合常数存在差异的主要原因.     

高浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用

利用红外和拉曼光谱技术研究了不同浓度LiClO₄/丙酮溶液中离子-溶剂和离子-离子的相互作用. 红外和拉曼光谱的分析表明, Li^＋与丙酮分子发生了强烈的相互作用, 导致丙酮C—C伸缩振动谱带、C＝O伸缩振动谱带等发生了分裂. Li^＋的溶剂化数随溶液浓度的增加逐渐降低, 在所研究的LiClO₄浓度范围(0.31～3.98 mol•kg^－1)内由3.4减小到1.9. 此外, 根据的谱带变化确定了溶液中存在的多种离子对的形式, 计算了缔合平衡常数, 并与电导实验结果进行了比较, 解释了这两种方法测定的离子缔合常数存在差异的主要原因.     

Nuclear magnetic resonance of donor atoms as a tool for determination of the structure of platinum metal complexes in solutions

Data on the NMR spectroscopy of C, N, O, Si, P, and Sn donor atoms of platinum metal complexes in solutions are surveyed. The chemical shift of a donor atom mainly depends on the ligand in the trans-position (due to the trans-effect). The chemical shift of a donor atom on a particular coordinate of the complex (coordinate shift, CSh) is an attribute of this coordinate and can be used to identify such a coordinate in platinum metal complexes and to determine the structures of complexes. Based on the known data, CSh diagrams were composed for ¹H, ¹³C, ¹⁴N, ¹⁷O, ¹⁹F, ³¹P, and ¹¹⁹Sn. Examples of using the CShs for determining the structures of platinum metal complexes in solutions are presented.     

A 13C, 15N and 77Se NMR Study of Some Diseleno Sulfonamides

¹³C, ¹⁵N and ⁷⁷Se NMR data are reported for ten title compounds. Some linear correlations of selenium, nitrogen and carbon chemical shifts values are described. A number of one- and two- bond ⁷⁷Se-¹³C coupling constants values are also given.     

Invertomers at nitrogen in aziridine carboxylates by mltltinuclear (1H,13C,17O,and15N) NMR study

A confrgurational and conformational study of NH, N-acetyl- and N-sulfonylaziridine carboxylates is performed by¹H ,¹³C,¹⁷O, and¹⁵N NMR spectroscopy. The presence of acetyl and su fonyl groups on the ring nitrogen atom seems to reduce greatly the configurational stability at nitrogen.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1226–1234, September, 1995.     

A multinuclear NMR study in the solid state and in solution of thallium(I) tris-(pyrazol-1-yl)borates (thallium scorpionates)

The ¹H, ¹³C and ¹⁵N NMR spectroscopic properties of six thallium tris-(pyrazol-1-yl)borates, including a tetrakis derivative, were determined. The results in solution were necessary to understand those, more complicated, in the solid state. A collection of ²⁰⁵Tl-¹⁵N and ²⁰⁵Tl-¹³C couplings was measured in the latter state. Among those, a very large coupling constant (between 194 and 282 Hz) has been measured on the carbon at the position 4 of the pyrazole ring in several compounds and particularly for the cyclobutyl derivative [Tl(Tp^Cbu)]. It has been assigned to a direct interaction of the 4-C-H ? Tl type and related to the X-ray structures, when available.     

Wege zu Si-funktionalisierten Organostannylsilanen

Summary Silicon substituted organostannyl silanes are formed by the reaction of stannylallyl silanes with triflic acid and from stannyl-hydrogen silanes and CHBr₃. The structures have been proved by NMR-investigations.

Herrn Prof. Dr.E. Hengge zum 65. Geburtstag gewidmet     

Phosphorus Derivatives of Natural Lactones. Synthesis of New Grosshemin Dialkylphosphonates

New phosphorus-containing derivatives of grosshemin were synthesized in 68-70% yield by reacting this guaianolide with dialkylphosphites. Their structures were established by IR, PMR, ¹³C NMR, and ³¹P NMR spectroscopies and two-dimensional ¹H-¹H NMR spectroscopy (COSY). The reaction of grosshemin with dialkylphosphites was found to be highly stereoselective.     

A comparative study of NMR chemical shifts of sparteine thiolactams and lactams

The ¹³C and ¹H NMR spectra of the four possible thiolactams of sparteine (1) were recorded and the thiolactam group effects were determined. Most of the effects are greater than those of the lactam group in the oxo analogs. A good linear correlation between the ¹³C chemical shifts of CS and those of CO was found. The effects could help in assignment of the spectra and determination of conformation of thiolactams and related thiocarbonyl compounds.     

Synthesis, characterization and solution behaviour of phosphoryl complexes of tin tetrafluoride

The preparation and characterization of a series of octahedral complexes [SnF₄L₂] (L = (Me₂N)₃PO (1), L = (R₂N)₂P(O)F; R = Me (2); Et (3) or L = R₂NP(O)F₂; R = Me (4); Et (5)) are described. These new adducts have been characterised by multinuclear (¹⁹F, ³¹P and ¹¹⁹Sn) NMR, IR spectroscopy and elemental analysis. The NMR data particularly the ¹⁹F NMR spectra showed that the complexes exist in solution as mixtures of cis and trans isomers. The solution behaviour of the complexes studied by variable temperature NMR in the presence of excess ligand indicated that, unlike in the SnCl₄ analogues, the ligand exchange at room temperature is slow for 1–3 and fast only for 4 and 5. The metal–ligand exchange barriers in [SnF₄L₂] and [SnCl₄L₂] systems were estimated and compared. The results indicate that in addition to the difference in the Lewis acidity between SnF₄ and SnCl₄ the nature of the substituents (fluorine atoms) on the phosphorus atom of the ligand can contribute considerably to the lability of the complex obtained.     

NMR spectra of 1,3,5-triazines with fluorinated substituents

The NMR spectra of a series of 1,3,5-triazines (1) in which one or more of the substituent groups are fluorinated are described, and the results are discussed in terms of bonding and geometry of the molecules. Remote effects of unsymmetrical substitution are observed in the fluorine-19 and carbon-13 spectra, in some molecules indicating restricted rotation about the bond joining an amino group to a ring carbon.     

Structural Assignment of Side Chain Liquid Crystalline Monomer and Polymer by 1-D and 2-D Solution NMR Studies

In the present study, the synthesis and characterization of a methacrylic-based side chain liquid crystalline monomer and its polymer were investigated with the aid of both 1-D and 2-D nuclear magnetic resonance (NMR) techniques. The mesophase characteristics of the monomer and polymer were determined by hot-stage optical polarized microscopy (HOPM). The nematic and smectic phases were observed for the monomer and polymer. Furthermore, ¹³C spin-lattice relaxation time measurements were performed on the above systems in order to monitor molecular dynamics. The present study provides an opportunity to carry out a systematic comparison of the evolution of structural as well as dynamical changes of the monomer and the polymer.