水合苯并—15—冠—5四溴合铟(Ⅲ)酸钠(NaInBr4)2(C14H20O5)3·2H2O的晶体结构

本文报道了在乙醇—氯仿混合溶剂中首次获得组份为(NaInBr₄)₂(C₁₄H₂₀O₅)₃·2H₂O的晶体配合物.用元素分析确定了其组份.通过红外光谱的研究证实配合物晶体中的阳离子与醚氧原子及水分子发生了配合作用。 用X-射线衍射法测定了配合物的晶体结构,晶体属单斜晶系,M=1755.3,a=14.393(8)Å,b=28.494(9)Å,c=15.191(8)Å,β=96.63(5)°,V=6189ų,D_c=1.88g·cm^-3,Z=4,空间群为C_2h⁵——P2₁/n。晶体结构研究表明不对称单位中包含两个配阳离子Na⁺(B15C5)(B15C5)代表C₁₄H₂₀O₅分子)。两个配阴离子InBr₄^-、两个H₂O分子和一个未被金属离子配合的B15C5分子。配合物的晶体结构测定结果对于阐明与该晶体相对应的萃取体系In(Ⅲ)/NaBr/B15C5—1,2C₂H₄Cl₂的萃取机理提供了理论依据。     

二氯·双(N, N-二乙基-2-辛硫基乙酰胺)合钯(Ⅱ)配合物的合成及其结构

在有机溶剂中合成了反式-[Pb(DEOTA)₂Cl₂],C₂₈H₅₈N₂O₂Cl₂S₂Pd,对配合物进行了组成分析、摩尔电导、差热-热重、紫外、红外等测试,并经X射线单晶结构分析,确定了配合物的结构.配合物晶体属单斜晶系,空间群C₂/ca=32.513(9)Å,b=12.174(3)Å,c=9.798(4)Å,β=106.27(3)°,V=3722(1)ų,Z=4,D_c=1.24g·cm^-3.     

η6—芳烃希土有机配合物的合成、结构及性能研究——Ⅰ. Sm(η6—C6H6)(AlCl4)3的合成及晶体结构

经过铝粉加热活化的AlCl₃与SmCl₃在苯中反应,得到了Sm(η⁶—C₆H₆)(AlCl₄)₃·C₆H₆单晶.其晶体属于三斜晶系,P1空间群,晶胞参数a=9.456(2)Å,b=9.765(3)Å,c=16.776(4)Å,α=96.00(2)°,β=93.76(2)°,γ=111.66(2)°,V=1422.55ų,Z=2.晶体结构是采用Patterson和Fourier合成法解出的,所有非氢原子的坐标及各向异性热振动参数经块矩阵最小二乘法修正,最后偏离因子R=0.031,R_ω=0.035.分子结构中,中心离子Sm(Ⅲ)与六个Cl原子及一个苯环上的六个C原子成键.Sm-C键平均距离2.92Å,Sm-Cl平均距离2.83Å.与希土相连的六个Cl原子,其中之五构成平面五边形,整个分子呈大致的五角双锥形.     

中性磷(膦)类希土萃合物的结构研究——Ⅱ.四(三苯基氧膦)合硫氰酸钕的合成及结构测定

合成了四(三苯基氧膦)合硫氰酸钕配合物,通过元素分析及分子量测定,确定了该配合物的化学式为Nd(NCS)₃·4ph₃P=O。经x射线单晶衍射测定了该配合物的结构,晶体属单斜晶系,P2₁/C空间群,晶体学参数如下: a=13.221(7)Å v=6943ų b=23.544(14)Å z=4 c=22.821(18)Å d实验值=1.375g/cm³ β=102.19(5)° d计算值=1.370g/cm³ F(0,0,0,0)=2924e 吸收系数μ=9.8cm^-1(MoK_a) 钕的配位数为七,三个NCS^-根以氮与钕配位,平均键长2.50Å,四个三苯基氧膦以膦酰基上的氧与钕配位,平均Nd—O键长2.39Å。分子具有近似的C₈对称性。     

希土季铵盐配合物的研究——Ⅴ.[(n-C4H9)4N]3Nd(NCS)6的晶体结构研究

合成了硫氰酸合希土酸四丁基季铵盐配合物,测定了它们的远红外光谱及部分配合物的中红外光谱,结果表明,配合物中的NCS^-是以氮原子与Ln³⁺配位。用X射线单晶衍射法测定了[(n-C₄H₉)₄N]₃Nd(NCS)₆晶体的结构,结果表明,该晶体属单斜晶系,C_c空间群,晶胞参数为:a=25.188(8)Å,b=13.320(6)Å,c=25.322(8)Å,β=121.30(2)°,晶胞体积V=7258.9ų,每一晶胞中有四个配合物分子,中心离子Nd³⁺与六个来自NCS^-的氮原子配位,这六个氮位于配位正八面体的六个顶角上,构成配阴离子Nd(NCS)₆^3-,它与三个[(n-C₄H₉)₄N]⁺以静电引力结合成中心分子,所以晶体为离子型晶体。     

[Tb(CH3COO)3(H2O)2]2的合成及其结构测定

2-羟基吡啶、希土高氯酸盐和乙酸钴在乙腈中反应,制备了九配位化合物[Tb(CH₃COO)₃·2H₂O]₂该晶体为三斜晶系,P1空间群,其晶胞参数为a=8.870(4)Å,b=9.247(1)Å,c=10.586(1)Å,α=65.13(1)°,β=64.43(2)°,γ=62.16(4)°,V=665.97ų,Z=1,F(000)=394。测定了配合物的红外光谱。讨论了它的生成机制。     

[Cu(H2O)(phen)2](CIO4)2的晶体结构

标题化合物晶体属三斜晶系;空间群为P₁;晶胞参数:a=8.182(2)Å,b=10.389(2)Å,c=16.261(5)Å,α=99.38(2)°,β=89.97(2)°,γ=113.18(2)°;Z=2,两个phen上的四个N原子和一个配位水中的O原子围绕中心体Cu原子形成一个畸变的三角双锥构型,配位水与阴离子ClO₄^-中的O原子形成氢键。     

单羟基桥连的双铜(Ⅱ)大环穴醚配合物[Cu2(OH)(ClO4)(C16H38N6)](ClO4)2·CHCl3的合成和结构

本文合成了单羟基桥连的双铜(Ⅱ)大环穴醚配合物[Cu₂(OH)(ClO₄)(C₁₆H₃₈N₆)](ClO₄)₂·CHCl₃,并测定与讨论了它的晶体结构.晶体属于正交晶系,空间群为D₂⁴-P2₁2₁2₁,晶胞参数:a=12.749(4)Å,b=14.361(3)Å,c=18.064(3)Å,V=3307.3(13)ų,Z=4.分子结构中单羟基桥连两个二价铜离子,Cu-O平均键长为1.935(6)Å,Cu-OH-Cu键角为135.2(2)°;铜原子的几何构型为畸变四方锥,配体的底面为穴醚的二乙三胺亚基的三个氮原子和一个羟基桥氧原子;顶点位置为高氯酸根的氧原子,因为该原子同时配位于另一个铜原子,所以分子的双铜中心存在第二个氧桥,即较弱的高氯酸根桥;Cu-O(ClO₃)距离分别为3.005(9)Å和2.806(8)Å.     

氯化二(羟胺根)·(羟胺—O)·水合氧钒(Ⅴ)[VO·(NH2O)2·(NH3O)·H2O]Cl的晶体结构

调节硫酸氧钒与盐酸羟胺溶液至pH～4制得的题目晶体属空间群P2₁/n,晶胞参数a=8.201,b=8.597,c=9.947A,β=93.00°,Z=4.结构解出精修后R因子为0.069.结果表明,不对称单位中二个羟胺根以侧接态与VO³⁺配位,另一羟胺取端接态以O占据V的第五赤道配位位置,配位水处于氧钒基强键反位,Cl^-则在配阳离子界外以平衡电荷,晶体对的化学式确证为[(VO³⁺)(NH₂O^-)₂(NH₃O)(H₂O)][Cl^-]     

三(1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5)二水合镱(Ⅲ)的晶体结构

本文合成了Yb(PMBP)₃(H₂O)₂,并用X-射线单晶衍射法测定了晶体和分子的结构.配合物的晶体为单斜晶系,空间群为P2₁/n,a=24.498(3)Å,b=14.735(3)Å,c=14.888(5)Å,β=101.14(2)Å,V=5285.1ų;Z=4.三个PMBP及两个水分子提供八个氧与镱配位形成四方反棱柱配位多面体.     

STRUCTURE,STEREOCHEMISTRY, AND MECHANISM OF FORMATION OF N-ACYLSULFILIMINES

Abstract

The methods for the preparation of sulfilimines are summarized, and the stereochemistry and electronic structure of N-acylsulfilmines are discussed. Sulfilimines have a non-planar structure, but the S^IV[sbnd]N bond character cannot be determined from their resolvability. N-Sulfonylsulfilimines (RR'SNSO₂Q) contain a delocalized S^IVNS^VI d bond system, the S^IVN and S^VIn bonds are of intermediate bond order. S^IV[sbnd]CH₃ hyperconjugation causes strong bond shortening. An asymmetric conformation of a sulfilimine containing two identical S^IV substituents was found in the crystalline state which could be accounted for theoretically. The rotation of the SN bond is not restricted in solution. The structure of N-carboacylsulfilimines (RR'SNCOQ) is strongly polar due to the strong NCO conjugation, and the instability of these compounds can be ascribed to the polar structure. The reaction between thioethers and chloramine-T is a nucleophilic substitution; the rate of the reaction is influenced by the nucleophilic character of the thioether sulfur atom. Thioether carboxylic acids are usually oxidized by chloramine-T and only give a sulfilimine if the carboxyl group is fixed sufficiently distant from the sulfur atom. The formation of sulfilimines from an optically active sulfoxide by the action of a sulfonamide (or N-sulfinylsulfonamide) proceeds via a trigonal bipyramidal intermediate with complete inversion. The intermediate of the sulfilimine synthesis starting from arylsulfonyl azides is a sulfonyl imene.     

煤中砷,铅,铍,铬等元素的存在状态

煤是由有机物和无机物组成的混合物。无机物按其在煤中的浓度大小可分为三类:(1)常量元素,在煤中浓度大于0.5%,如Si,Al,Fe,Ca等。(2)次要元素,约占煤的0.02%—.5%,包括K,Mg,Na,Ti,有时还有P,Ba等。(3)微量元素,在煤中浓度<0.02%,这类元素目前已测出60种左右。60年代以来,基于能源需求的增加,国内外煤炭消耗量都很大,考虑到有害的微量元素对环境的污染,国外进行了大量的煤     

关于二元酸与二元醇的聚酯反应和酯化与水解反应动力学

关于二元酸与二元醇的聚酯反应动力学,Flory和等人都会做过研究,唐敖庆等在较广泛的实验基础上提出氢离子催化机理及其动力学.酯化机理为:     

THERMOCHEMISTRY OF HETEROATOMIC COMPOUNDS,XX. THEORETICAL CALCULATIONS OF THE VAPORIZATION ENTHALPIES OF ALKYLARSINES,STIBINES, AND BISMUTHINES

The vaporization enthalpies (ΔH _vap ) of 26 primary, secondary, and tertiary alkylarsines, stibines, and bismuthines were calculated using the Trouton and Wadso equations and the first-order topological solvation index, ¹ χ ^S . The contributions to vaporization enthalpy for ─AsH ₂ (16.6 ± 0.2), > AsH (16.7 ± 0.1) groups and As(III)-atom in R ₃ As (13.7 ± 1.0), ─SbH ₂ (22.0 ± [2.0]), > SbH (19.0 ± [2.0]) groups and Sb(III)-atom in R ₃ Sb (12.7 ± 3.5), ─BiH ₂ (26.3 ± [2.2]), > BiH (24.3 ± [2.2]) groups and Bi(III)-atom in R ₃ Bi (16.2 ± 3.1 kJ mol^?1 ) were calculated.     

MAGNETOSTRATIGRAPHY OF PERMO-TRIASSIC BOUNDARY SECTION OF MEISHAN OF CHANGXING,ZHEJIANG

A hundred and eleven samples were collected from the Permian-Triassic boundarysection of Meishan (31.1°N, 119.7°E) which includes the Changxing Formation of thelate Permian and the Qinglong Formation of early Triassic. The thickness of the sectionis about 60 m. Paleomagnetic results indicate that six normal and reversed polarity zoneswere recorded in the section which all belong to the Illawarra mixed interval. Theboundary of Permo-Triassic lies at 1.2 m (or 2.7 m) above the bottom of normal polarityzone V. The magnetic minerals in the rocks of the lower part of the Changxing Forma-tion mainly are goethite, haematite and titaniferous magnetite while in the upper part ofthe formation are chiefly titanomagnetite and magnetite, goethite is secondary. Magne-tite and haematite as the main magnetic minerals were included in marl and mudstone ofthe Qinglong Formation. Based on the results of the magnetically stable samples thepaleopole position of 50.7°N, 230.3°E was obtained, meanwhile, the paleolatitude     

OLEFIN SYNTHESIS USING LITHIUM DERIVATIVES OF N,N,N',N'-TETRAMETHYLDIAMIDES OF ARYLMETHANEPHOSPHONIC ACIDS

Abstract

The reaction of lithium derivatives of N,N,N',N'-tetramethyldiamides of arylmethanephosphonic acids (1-Li) with aldehydes 2 is studied. It is found that under certain reaction conditions (THF, 5 hrs at -70°C and then allowing to warm to room temperature) the aldol stage of the reaction is highly stereoselective, only erythro adducts (2-hydroxyphosphonamides) 3, 4 being formed in 47–75% yields. By heating of 3 and 4 in neutral medium the corresponding (Z)-olefins 5, 6 are obtained (yields 64–74%). It is established that an acid catalyzed olefination of 2-hydroxyphosphonamides is also possible, but the reaction is not stereospecific.     

PHOTOSENSORY BEHAVIOR OF A BACTERIORHODOPSIN-DEFICIENT MUTANT, ET-15, OF Halobacterium halobium

– Halobacterium halobium , strain ET-15, which does not contain detectable amounts of bacteriorhodopsin (BR) shows behavioral responses to UV and yellow-green light. Attractant stimuli. i.e. light-increases in the yellow-green range or light-decreases in the UV, suppress the spontaneous reversals of the swimming direction for a certain time. Repellent stimuli, i.e. light-decreases in the yellow-green range or light-increases in the UV, elicit an additional reversal response after a few seconds. Action spectra of both sensory photosystems, PS 370 and PS 565, were measured with attractant as well as with repellent stimuli. As in BR-containing cells, maximal sensitivity was always found at 370 nm for the UV-system and at 565 nm for the long-wavelength system. Fluence-response curves at 370 and 565 nm obtained with strain ET-15 and with a BR-containing strain show that the sensitivity of both photosystems is not reduced in the absence of BR. It is concluded that BR is required neither for PS 565 nor for PS 370. Instead retinal-containing pigments different from BR have to be assumed to mediate photosensory behavior.     

延胡索己素、壬素、癸素和子素的结构鉴定

延胡索(Corydalis turtshnninovii Bess.f.Yanhusuo Y.H.Chou et C.C.Hsü)^*块茎又称元胡,能活血散瘀,利气止痛.药用主要作为镇痛药.赵承嘏^[1]曾从其块茎中分得十三种生物碱,分别命名为延胡索素甲、乙、丙、丁、戊、己、庚、辛、壬、癸、子、丑和寅.其中甲素鉴定为紫堇碱,丙素为普鲁托品,丁素为l-四氢黄连碱,戊素为dl-四氢黄连碱,己素为l-紫堇单酚碱,庚素为d-紫堇球碱,寅素为a-别隐品碱.黄鸣龙^[2]除证明乙素为dl-四氢巴马汀外,还分得黄连碱和去氢紫堇碱.     

A THEORETICAL TREATMENT OF THE SULFUR-CONTAINING ANALOGS OF CYCLOBUTADIENE,CYCLOOCTATETRAENE, BUTALENE,AND OCTALENE

Abstract

Several coordination complexes of cyclobutadiene (I) have been prepared (e.g., cyclobutadiene iron tricarbonyl [1]) and cyclooctatetraene (II) is a well-known compound (for a potentially planar form of cyclooctatetraene, see [2]). Although butalene [3] (III) has not been synthesized so far, octalene (IV) has been obtained by Vogel and co-workers [4,5]. Recently we have carried out a theoretical study of the physical and chemical properties of butalene (III) and octalene (IV), and of the various annelated butalenes and octalenes [6,7] using the HMO and SCF-MO (PPP) quantum-chemical methods as well as the structure-resonance theory and graph theoretical methods. Numerous theoretical data are available in the literature on cyclobutadiene (I) and cyclooctatetraene (II).