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Crystal structure of arsenic trichloride–trimethylamine, AsCl3,NMe3 三氯化砷三甲胺、AsCl3、NMe3的晶体结构
Pub Date : 1971-01-01 DOI: 10.1039/J19710000836
M. Webster, S. Keats
The title compound has been examined by single-crystal X-ray diffraction and crystallises in the space group P21/c with Z= 4 in a unit cell of dimensions a= 6·14, b= 10·33, c= 14·85 A, and β= 107·0°. The structure consists of discrete AsCl3,NMe3 molecules which may be considered to be based on trigonal bipyramidal arsenic co-ordination and the photographically estimated three-dimensional data were refined to R 0·083.
通过x射线单晶衍射对该化合物进行了检测,发现该化合物在Z= 4的P21/c空间群中,在尺寸为a= 6.14, b= 10.33, c= 14.85 a, β= 107·0°的晶胞中结晶。该结构由离散的AsCl3,NMe3分子组成,可以认为是基于三角双锥体砷配位,并将图像估计的三维数据精确到r0·083。
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引用次数: 7
Crystal and molecular structure of NN′-ethylenebis(salicylideneiminato)-ethylcobalt(III) NN′-乙烯双(水杨基氨基)-乙基钴(III)的晶体结构和分子结构
Pub Date : 1971-01-01 DOI: 10.1039/J19710002720
M. Calligaris, D. Minichelli, G. Nardin, L. Randaccio
The crystal and molecular structure of NN′-ethylenebis(salicylideneiminato)ethylcobalt(III), [EtCo(salen)], has been determined from three-dimensional X-ray data by the heavy-atom method. The crystals are monoclinic with a= 13·97, b= 7·39, c= 18·96 A, β= 127·2°, Z= 4, space group P21/c. Anisotropic least-squares refinement gave R 0·085 for 1762 independent reflexions. The crystals are built up by centrosymmetric dimeric units, dimerisation being achieved through the co-ordination of the cobalt atoms by an oxygen atom of the other [EtCo(salen)] unit (Co–O 2·342 ± 0·003 A).The co-ordination polyhedron of the cobalt atoms is represented by a distorted octahedron. The axial positions are occupied by an oxygen atom of the other Co(salen) unit and by the σ-bonded ethyl group (Co–C 1·990 ± 0·007 A); the four equatorial positions are occupied by the quadridentate salen ligand with Co–O 1·901 ± 0·005 and 1·935 ± 0·004 A and Co–N 1·886 and 1·880 ± 0·006 A. Some properties of salen-type ligands and the trans-influence in the octahedral cobalt complexes are discussed.
用重原子法从三维x射线数据中测定了NN′-乙烯双(水杨基氨基)乙基钴(III) [EtCo(salen)]的晶体和分子结构。晶体为单斜晶型,a= 13.97, b= 7.39, c= 18.96 a, β= 127·2°,Z= 4,空间群P21/c。各向异性最小二乘改进得到了1762个独立反射的r0·085。晶体由中心对称的二聚体单元组成,二聚化是通过钴原子与另一个[EtCo(salen)]单元(Co-O 2·342±0.003 A)的氧原子的配位实现的。钴原子的配位多面体由一个扭曲的八面体表示。轴向位置由另一个Co(salen)单元的氧原子和σ键乙基(Co - c1·990±0·007 A)占据;四个赤道位置为四齿salen配体,Co-O为1·901±0.005和1·935±0.004 A, Co-N为1·886和1·880±0.006 A。讨论了salen型配体的一些性质及其在八面体钴配合物中的反式影响。
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引用次数: 10
Reactions between the gallium ‘dihalides’ and ethanol 二卤化镓和乙醇之间的反应
Pub Date : 1971-01-01 DOI: 10.1039/J19710002315
J. Oliver, I. J. Worrall
The reaction between Ga2X4(X = Cl or Br) and ethanol is complex. Results indicate that at 0 °C the principal reaction is, Ga2X4+ 3EtOH → Ga(OEt)2X + GaX3,EtOH + H2 and at 25 °C, Ga2X4+ 2EtOH → 2Ga(OEt)X2+ H2 Cryoscopic molecular-weight, mass-spectra, and 1H n.m.r. data show that the monoethoxygallium dihalides occur in at least three forms: tetramer, trimer, and dimer. The tetramer (which is thought to contain six-co-ordinate gallium) is thermally unstable and is readily converted to lower forms.
Ga2X4(X = Cl或Br)与乙醇的反应是复杂的。结果表明,在0°C时,主要反应为Ga2X4+ 3EtOH→Ga(OEt)2X + GaX3,EtOH + H2;在25°C时,Ga2X4+ 2EtOH→2Ga(OEt)X2+ H2。低温分子量、质谱和1H nmr数据表明,单乙氧二卤化镓以四聚体、三聚体和二聚体的形式存在。四聚体(被认为含有六配位镓)是热不稳定的,很容易转化为较低的形式。
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引用次数: 2
The standard potentials of silver–silver halide electrodes and ion solvation in dimethyl sulphoxide–water mixtures at 25 °C 银-卤化银电极的标准电位和离子溶剂化在二甲基亚砜-水混合物中的25°C
Pub Date : 1971-01-01 DOI: 10.1039/J19710002932
K. H. Khoo
Standard e.m.f.s of the cells H2|HX|AgX–Ag (X = Cl, Br, or I) in 10, 60, 70, and 80%(w/w) dimethyl sulphoxide–water mixtures are reported. These, together with values for mixtures of other compositions determined earlier, were used to calculate the molar free energies of transfer of the halogen acids from water to the mixed solvents. Single-ion values were derived therefrom by use of the extrathermodynamic assumptions of Feakins et al. and discussed in terms of ion solvation. It is shown that the solvophilicity of the ions is largely determined by their acid–base' interactions with the solvent molecules. The structural features of the solvents are briefly discussed.
报道了电池H2|HX| AgX-Ag (X = Cl, Br,或I)在10、60、70和80%(w/w)二甲亚砜-水混合物中的标准电磁脉冲。这些值,连同先前测定的其他成分的混合物的值,被用来计算卤素酸从水到混合溶剂转移的摩尔自由能。单离子值是通过Feakins等人的超热力学假设推导出来的,并在离子溶剂化方面进行了讨论。结果表明,离子的亲溶剂性在很大程度上取决于它们与溶剂分子的酸碱相互作用。简要讨论了溶剂的结构特点。
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引用次数: 10
Thermal diffusion in the n-heptane–benzene system at 25°C 25℃下正庚烷-苯体系的热扩散
Pub Date : 1971-01-01 DOI: 10.1039/J19710000307
J. Demichowicz-Pigoniowa, M. Mitchell, H. Tyrrell
Thermal diffusion factors and heats of transfer have been determined for liquid mixtures of n-heptane and benzene over a wide range of concentrations at 25 °C. A pure Soret effect cell, with a liquid layer less than 1 mm thick, was used. The results agree well with some recently published data obtained by Korsching using a different method.
在25℃下,测定了正庚烷和苯的液体混合物在宽浓度范围内的热扩散系数和传递热。采用纯Soret效应电池,液层厚度小于1mm。结果与Korsching用不同的方法得到的最近发表的一些数据吻合得很好。
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引用次数: 15
A new polynuclear oxocarbonyl containing six osmium atoms 含有六个锇原子的一种新的多核氧羰基
Pub Date : 1971-01-01 DOI: 10.1039/J19710002038
C. W. Bradford, R. Nyholm
A new polynuclear oxocarbonyl of osmium having the formula Os6O6(CO)16 has been isolated from the products obtained during the synthesis of Os3(CO)12. The mass and i.r. spectra of the new compound and of Os4O4(CO)12 are reported and compared.
从Os3(CO)12的合成产物中分离出一种新的锇多核氧羰基,分子式为Os6O6(CO)16。报道并比较了新化合物与Os4O4(CO)12的质量和红外光谱。
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引用次数: 4
Growth of crystals from the gas phase. Part II. Diffusional limitations and interfacial stability in crystal growth by dissociative sublimation, with an inert third gas present 气相晶体的生长。第二部分。存在惰性第三气体的解离升华晶体生长中的扩散限制和界面稳定性
Pub Date : 1971-01-01 DOI: 10.1039/J19710000001
M. M. Faktor, R. Heckingbottom, I. Garrett
The quantitative treatment of interfacial stability in crystal growth from the vapour phase, presented in a previous paper, has been extended to cover (1) large temperature differences between source and seed, (2) arbitrary temperature profiles, and (3) an inert third species in the gas phase. The effect on the growth rate and critical growth rate of altering the temperature profile has been investigated and found to be small if the slope at the growing interface is above about 10 K cm–1. The influence of small quantities of inert gas on the temperature difference corresponding to the critical growth rate is shown to provide a useful stabilising effect against unavoidable temperature fluctuations. At the same time, the partial pressure ratio α of the active components becomes a less sensitive function of the distance along the growth capsule. The treatment is general; however, the familiar case of cadmium sulphide is included as an illustration and for comparison with our previous results.
在之前的一篇论文中提出的从气相开始晶体生长的界面稳定性的定量处理,已经扩展到涵盖(1)源和种子之间的大温差,(2)任意温度分布,以及(3)气相中的惰性第三种。研究了温度分布对生长速率和临界生长速率的影响,发现当生长界面的斜率大于10 K cm-1时,温度分布对生长速率和临界生长速率的影响很小。少量惰性气体对与临界生长速率相对应的温差的影响,对不可避免的温度波动提供了有用的稳定作用。同时,活性组分的分压比α随生长囊距离的变化变得不那么敏感。治疗是一般的;然而,我们所熟悉的硫化镉的情况是作为一个例证,并与我们以前的结果进行比较。
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引用次数: 14
The reactions of ethylene and acetylene at the surface of solutions of barium in liquid sodium 乙炔和乙炔在钠溶液中钡表面的反应
Pub Date : 1971-01-01 DOI: 10.1039/J19710001708
C. C. Addison, M. Hobdell, R. J. Pulham
The addition of barium to liquid sodium modifies the reactions of the liquid metal with simple hydrocarbons. The reactions of 4·6 atoms % solutions of barium in liquid sodium with acetylene and ethylene have been studied at 100, 150, and 200 °C and at starting pressures up to 18 cmHg. Ethylene reacts with this solution to give a solid acetylide and hydrogen, but hydrogenation to ethane also occurs to a small extent. Reaction of acetylene is much slower (by a factor of about 50) than with liquid sodium alone. Breaks in pressure–time curves are interpreted in terms of adsorption and reaction of acetylene, ethylene, and hydrogen at the metal surface.
在液态钠中加入钡改变了液态金属与简单碳氢化合物的反应。在100、150、200℃和18 cmHg的启动压力下,研究了4·6原子%的钡溶液在钠液中与乙炔和乙烯的反应。乙烯与该溶液反应生成固体乙炔和氢,但也有少量的氢化反应生成乙烷。与单独与液态钠反应相比,乙炔的反应要慢得多(大约慢50倍)。压力-时间曲线的断裂用乙炔、乙烯和氢在金属表面的吸附和反应来解释。
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引用次数: 0
The preparation and characterization of the µ-amido-µ-oxalato-bis[tetra-amminecobalt(III)] complex, and the kinetics of reduction with Cr2+ and V2+ µ-氨基-µ-草草酸-双[四氨基钴(III)]配合物的制备、表征及Cr2+和V2+还原动力学
Pub Date : 1971-01-01 DOI: 10.1039/J19710003651
K. L. Scott, Mark M. Green, A. Sykes
The chloride salt of the protonated form of the µ-amido-µ-oxalato-bis[tetra-amminecobalt(III)] complex, has been prepared and characterized. The perchlorate salt has also been prepared and it would appear that the oxalate [graphic omitted] bridge is only 50% protonated in this solid. From spectrophotometric measurements on the complex in acidic solutions at 15–45°, µ= 2·0M(LiClO4), values of the protonation constant K= 18 ± 2 l mol–1 have been determined. Reduction with chromium(II), 2Cr2++(CoIII)2→ 2Co2++(CrIII)2, proceeds in two stages, each involving attack of the chromium(II) and reduction of cobalt(III). Both protonated (ka) and unprotonated (kb) forms participate in the first stage of the reaction (k1), and the rate law (Cr2+ in large excess) is as in (i) [graphic omitted]. At 25° and µ= 2·0M(LiClO4), ka= 1·45 ± 0·07 l mol–1 s–1, and kb= 35·2 ± 0·4 l mol–1 s–1. The second stage of the reduction is independent of [H+] as in (ii) [graphic omitted] and k2= 1·88 ± 0·05 l mol–1 s–1 at 25°. Information regarding the spectrum of the intermediate and final product has been obtained. The reduction with V2+ also proceeds in two stages, the first of which is directly measurable. The rate law observed is of the same form as (i), and again both the protonated (kc) and unprotonated (kd) forms are reactive. At 25° and µ= 2·0M(LiClO4), kc= 3·51 ± 0·04 l mol–1 s–1 and kd= 22·7 ± 0·4 l mol–1 s–1. Activation parameters have been obtained for ka, kb, k2, kc, and kd.
制备了质子化形式的µ-氨基-µ-草草酸二[四氨基钴(III)]配合物的氯盐,并对其进行了表征。高氯酸盐也已制备,草酸盐桥在该固体中似乎只有50%质子化。在15-45°,µ= 2.0 m (LiClO4)的酸性溶液中,通过分光光度法测定了配合物的质子化常数K= 18±2l mol-1。铬(II)的还原,2Cr2++(CoIII)2→2Co2++(CrIII)2,分两个阶段进行,每个阶段都涉及铬(II)的攻击和钴(III)的还原。质子化(ka)和未质子化(kb)形式都参与了反应的第一阶段(k1),速率定律(过量的Cr2+)如(i)所示[图略]。在25°,µ= 2.0 m (LiClO4)下,ka= 1.45±0.07 l mol-1 s-1, kb= 35.2±0.4 l mol-1 s-1。第二阶段的还原与[H+]无关,如(ii)[图略],在25°时k2= 1.88±0.05 l mol-1 s-1。获得了中间产物和最终产物的光谱信息。V2+的减少也分两个阶段进行,第一个阶段是直接可测量的。所观察到的速率定律与(i)的形式相同,同样,质子化(kc)和未质子化(kd)的形式都是活性的。在25°,µ= 2.0 m (LiClO4)下,kc= 3.51±0.04 l mol-1 s-1, kd= 22.7±0.4 l mol-1 s-1。得到了ka、kb、k2、kc和kd的活化参数。
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引用次数: 1
Studies on Grignard reagents. Part III. Proton resonance spectra of alkyl and aryl Grignard reagents 格氏试剂的研究。第三部分。烷基和芳基格氏试剂的质子共振谱
Pub Date : 1971-01-01 DOI: 10.1039/J19710000184
D. F. Evans, G. Fazakerley
Proton resonance spectra are reported for a variety of Grignard reagents in a number of different solvents, and also for mixtures with the corresponding bis-alkyl-and-aryl-magnesiums. At low temperatures chemical exchange of alkyl or aryl groups is slow on a proton resonance time-scale. The position of the Schlenk equilibrium, for which quantitative data are presented, depends very markedly on the alkyl or aryl group and on the solvent. Alkyl or aryl exchange is slower in strongly co-ordinating solvents.
质子共振光谱报道了各种格氏试剂在许多不同的溶剂中,以及与相应的双烷基和芳基镁的混合物。在低温下,烷基或芳基的化学交换在质子共振时间尺度上是缓慢的。施伦克平衡的位置,提供了定量数据,很大程度上取决于烷基或芳基和溶剂。烷基或芳基交换在强配位溶剂中较慢。
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引用次数: 14
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Journal of The Chemical Society A: Inorganic, Physical, Theoretical
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