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Kinetics of solvent exchange and ligand substitution reactions of metal ions in relation to structural properties of the solvent 溶剂交换和金属离子配体取代反应动力学与溶剂结构性质的关系
Pub Date : 1971-01-01 DOI: 10.1039/J19710002198
H. P. Bennetto, E. Caldin
Activation parameters of solvent exchange and ligand substitution reactions of metal ions are discussed in relation to structural properties. Solvent exchange is treated as a particular case of ligand substitution. A general relation between enthalpy and entropy of activation is shown to hold for both types of reaction at divalent metal ions for a wide variety of solvents and ligands, after corrections have been made for ligand-field stabilisation. Water occupies a middle position in the range of solvents. The results are interpreted in terms of a structural model for a solvated ion in solution, based on that of Frank and Wen.
讨论了金属离子的溶剂交换和配体取代反应的活化参数与结构性质的关系。溶剂交换被视为配体取代的一种特殊情况。在对配体场稳定性进行校正后,焓和激活熵之间的一般关系表明,在各种溶剂和配体中,两种类型的二价金属离子反应都适用。水在溶剂中处于中间位置。在Frank和Wen的基础上,用溶液中溶剂化离子的结构模型对结果进行了解释。
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引用次数: 41
The reactions of acetylene and propyne at the surface of liquid sodium 乙炔和丙炔在液态钠表面的反应
Pub Date : 1971-01-01 DOI: 10.1039/J19710001704
C. C. Addison, M. Hobdell, R. J. Pulham
The reactions of acetylene and propyne at the surface of liquid sodium have been studied at 110, 150, and 200 °C. A fresh metal surface was maintained by magnetic stirring, so arranged that the metal poured continuously over a baffle plate. The course of the reactions was followed from pressure–time curves, and the i.r. spectra of the gas phase. At 110 °C, propyne reacts smoothly according to equation (i) and all hydrogen atoms produced at the 3MeCCH + 2Na → 2NaCCMe + MeCHCH2(i), surface of the metal are employed in the hydrogenation of propyne to propene. A smaller effect (probably polymerisation) also becomes evident at 200 °C. The behaviour of acetylene is markedly different, and the reaction proceeds in two stages. In the first, disodium acetylide (but no hydrogen acetylide) is formed, and the gas phase consists of hydrogen and ethylene in the ratio 1·42 : 1 at 150 °C. No ethane was detected. The second stage involves reaction of hydrogen with sodium metal, and this does not commence until all acetylene is removed from the gas phase. The results are discussed qualitatively in terms of the relative absorption of the gases at the sodium surface, which may have some analogies with their absorption coefficients at transition-metal surfaces.
研究了乙炔和丙炔在110℃、150℃和200℃液钠表面的反应。磁搅拌使金属表面保持新鲜,使金属连续地倒在挡板上。用压力-时间曲线和气相红外光谱跟踪了反应过程。在110℃时,丙烯根据式(i)进行了平稳反应,金属表面3MeCCH + 2Na→2NaCCMe + MeCHCH2(i)生成的氢原子全部用于丙烯加氢生成丙烯。在200°C时,较小的效应(可能是聚合)也变得明显。乙炔的反应行为明显不同,反应分两个阶段进行。第一种反应生成乙酰二钠(但不生成乙酰氢),在150℃下气相由氢和乙烯组成,比例为1·42:1。没有检测到乙烷。第二阶段涉及氢与金属钠的反应,直到所有乙炔从气相中除去后才开始。结果定性地讨论了气体在钠表面的相对吸收,这可能与它们在过渡金属表面的吸收系数有一些相似之处。
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引用次数: 3
Crystal structures of the non-isomorphous potassium and rubidium acid salts of 5-bromo-3-hydroxy-6-methyluracil 5-溴-3-羟基-6-甲基尿嘧啶非同形钾、铷酸盐的晶体结构
Pub Date : 1971-01-01 DOI: 10.1039/J19710002077
M. Truter, B. Vickery
Three-dimensional X-ray crystal structure analyses have been carried out on the compounds MIH[C5H4BrN2O3]2. For MI= K, Z= 4 in a monoclinic unit cell having a= 14·884, b 14·779, c= 7·135 A, β= 97·61°, and space group l2/c. The cation lies on a two-fold axis which relates two anionic moieties with a short [2·42(2)A] hydrogen bond between oxygen atoms. The potassium is ten-co-ordinate and K–O distances range from 2·739–3·105(9)A, mean 2·944 A; each uracil chelates two potassium ions and makes one contact with a third. These K–O contacts and the ‘symmetrical’ hydrogen bond hold the structure in columns along the needle axis of the crystal, c. Hydrogen bonds N–H ⋯ O, 2·73(1)A, hold the columns together in the other two directions.For M1= Rb, Z= 4 in an orthorhombic unit cell having a= 5·995, b= 21·825, c= 11·932 A and space group lba2. The rubidium ion is on a two-fold axis and is six-co-ordinated by a trigonal prism of oxygen atoms at distances from 2·93–3·00(1)A, mean 2·977 A. The three oxygen atoms of one uracil moiety make contact with different rubidium ions and each oxygen with only one rubidium. Metal–oxygen contacts and hydrogen bonds [N–H ⋯ O 2·88(3) and O ⋯ O 2·42(5)A] hold the structure in layers; shortest contacts between the layers are Br ⋯ Me 3·59 and Br ⋯ Br 3·68 A. The shorter hydrogen bond joins N(3) oxygen atoms across a two-fold axis.The differences in structure are correlated with differences in the i.r. spectra.
对化合物MIH[C5H4BrN2O3]2进行了三维x射线晶体结构分析。在a= 14.884, b = 14.779, c= 7.135 a, β= 97.61°,空间群l2/c的单斜胞中,MI= K, Z= 4。阳离子位于双轴上,它连接两个阴离子,氧原子之间有一个短的[2·42(2)a]氢键。钾为十坐标,K-O距离为2.739 ~ 3.105 (9)A,平均为2.944 A;每个尿嘧啶螯合两个钾离子,并与第三个钾离子进行一次接触。这些K-O接触和“对称”氢键沿着晶体的针轴将结构保持在柱中,c。氢键N-H⋯O, 2,73 (1)A,将柱在其他两个方向上保持在一起。对于具有a= 5·995,b= 21·825,c= 11·932 a和空间群lba2的正交晶胞中M1= Rb, Z= 4。铷离子位于双轴上,在距离为2.93 - 3.00 (1)a,平均为2.977 a的氧原子的三角棱镜处六坐标。一个尿嘧啶部分的三个氧原子与不同的铷离子接触,每个氧只与一个铷离子接触。金属-氧接触和氢键[N-H⋯O 2·88(3)和O⋯O 2·42(5)A]保持层状结构;层间接触最短的是Br⋯Me 3·59和Br⋯Br 3·68 A。较短的氢键将N(3)个氧原子连接在双轴上。结构上的差异与红外光谱上的差异有关。
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引用次数: 3
Magnetic double-resonance study of some derivatives of tungsten hexafluoride and tungsten oxotetrafluoride 六氟化钨和氧化四氟化钨衍生物的双磁共振研究
Pub Date : 1971-01-01 DOI: 10.1039/J19710000948
W. Mcfarlane, A. M. Noble, J. M. Winfield
The compounds WF6–n(OR)n(R = Me, n= 1–5; R = Ph, n= 1,2), WOF4L [L = Me2O or (MeO)2P(O)Me] and (MeO)3PMe+WOF5– have been studied by use of 19F–{183W}, 19F–{19F}, 1H–{19F}, and 1H–{31P} double-resonance techniques. 183W Chemical shifts are reported and the factors affecting these and the 19F shifts are discussed. By similar techniques WOF4,OS(OMe)2 and the µ-fluoro-bis[oxotetrafluorotungstate(VI)] anion, W2O2F9–, have been identified as products from the reaction of WF5OMe with (MeO)2SO. The coupling constants 2J(FcFt), 1J(FcW), and 1J(FtW)(Fc,Ft, cis and trans respectively to oxygen) all have the same sign in WF5OR and cis-WF4(OMe)2 but 1J(FcW) is of opposite sign to J(FcW) and J(FcFt) in WOF5– and W2O2F9–.
化合物WF6-n (OR)n(R = Me, n= 1-5;采用19F - {183W}、19F - {19F}、1H - {19F}和1H - {31P}双共振技术研究了R = Ph, n= 1,2)、WOF4L [L = Me2O或(MeO)2P(O)Me]和(MeO)3PMe+WOF5 -。报道了183W的化学位移,讨论了影响这些变化的因素和19F的位移。通过类似的技术,确定了WOF4、OS(OMe)2和µ-氟双[氧四氟钨酸盐(VI)]阴离子W2O2F9 -是WF5OMe与(MeO)2SO反应的产物。耦合常数2J(FcFt)、1J(FcW)和1J(FtW)(分别对氧为Fc、Ft、顺式和反式)在WF5OR和顺式- wf4 (OMe)2中符号相同,但在WOF5 -和W2O2F9 -中,1J(FcW)与J(FcW)和J(FcFt)符号相反。
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引用次数: 31
Structural and mechanistic studies of co-ordination compounds. Part II. Preparation, aquation, and base hydrolysis of trans-chloronitro- and trans-bromonitro-tetra-amminecobalt(III) cations 配位化合物的结构和机理研究。第二部分。反氯硝基和反溴四胺钴(III)阳离子的制备、水化和碱水解
Pub Date : 1971-01-01 DOI: 10.1039/J19710002151
C. Poon, H. Tong
The preparation and characterization of trans-[Co(NH3)4NO2Cl]+ and trans-[Co(NH3)4NO2Br]+ cations are described. The assignment of geometric configuration is based on 1H n.m.r. spectroscopy. The kinetics of the aquation and base hydrolysis of these two complex cations have been studied over a range of temperature. The first-order aquation rate constants are greater than those of the corresponding bis(ethylenediamine) and 1,4,8,11-tetra-azacyclotetradecane complexes, whereas the second-order base hydrolysis rate constants are less. These results are consistent with the kinetic nephelauxetic effect of these amine ligands on the central cobalt(III) ion. Unimolecular reaction mechanisms are assigned to these reactions.
介绍了反式[Co(NH3)4NO2Cl]+和反式[Co(NH3)4NO2Br]+阳离子的制备和表征。几何构型的分配是基于1H核磁共振光谱。在一定温度范围内研究了这两种络合阳离子的水化和碱水解动力学。一阶水解速率常数大于二乙二胺和1,4,8,11-四氮杂环十四烷配合物的水解速率常数,而二阶碱水解速率常数较小。这些结果与这些胺配体对中心钴(III)离子的动力学抑制作用一致。这些反应都有单分子反应机理。
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引用次数: 4
The vibrational spectra of systems containing linear or non-linear M–O–M linkages 包含线性或非线性M-O-M连杆系统的振动谱
Pub Date : 1971-01-01 DOI: 10.1039/J19710003569
I. R. Beattie, M. Gall
Using simple models for calculation it is shown that light atom M–O–M systems can possess ‘pseudo-linear’ vibrational characteristics until the interbond angle closes beyond the region of 140°.
用简单的模型计算表明,轻原子M-O-M体系在键间角关闭超过140°区域之前具有“伪线性”振动特性。
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引用次数: 7
Trimethylsilyl derivatives for the study of silicate structures. Part II. Orthosilicate, pyrosilicate, and ring structures 用于硅酸盐结构研究的三甲基硅基衍生物。第二部分。正硅酸盐、焦硅酸盐和环状结构
Pub Date : 1971-01-01 DOI: 10.1039/J19710000686
J. Götz, C. R. Masson
A direct method of trimethylsilylation reported previously for hemimorphite was applied to other silicates with well-defined structures. For anhydrous minerals the presence of water in the reaction medium was essential for trimethylsilylation. The effects of water and of time, temperature, and concentration of reagents on the trimethylsilylation were studied. A unified procedure was developed for conversion of orthosilicates to trimethylsilyl derivatives of the anion SiO44–, pyrosilicates to trimethylsilyl derivatives of Si2O76–, and silicates with a tetrameric ring structure to trimethylsilyl derivatives of Si4O128–, and for determination of these structures by gas–liquid partition chromatography.
一种直接的三甲基硅基化方法先前报道了半亚铁的应用于其他具有明确结构的硅酸盐。对于无水矿物,水在反应介质中的存在对于三甲基硅基化是必不可少的。研究了水、时间、温度和试剂浓度对三甲基硅基化反应的影响。建立了一套统一的程序,用于将正硅酸盐转化为阴离子SiO44 -的三甲基硅基衍生物,将焦硅酸盐转化为Si2O76 -的三甲基硅基衍生物,将四聚环结构的硅酸盐转化为Si4O128 -的三甲基硅基衍生物,并通过气液分配色谱法测定这些结构。
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引用次数: 36
Reactions of quinolin-8-ol with covalent halides. Part VI. Bis-π-cyclopentadienyldihalides of titanium, zirconium, and hafnium 喹啉-8-醇与共价卤化物的反应。第六部分:钛、锆、铪的双π-环戊二烯基二卤化物
Pub Date : 1971-01-01 DOI: 10.1039/J19710002487
J. Charalambous, M. Frazer, W. Newton
The complexes halogenocyclopentadienyldiquinolin-8-olatometal(IV), C5H5MXox2(M = Ti, Zr; X = Cl, Br and M = Hf, X = Cl), have been prepared by the direct interaction of quinolin-8-ol (oxH) and dihalogenobis(cyclopentadienyl)metal(IV)[(C5H5)2MX2] in acetonitrile solution at room temperature. Reactions of these complexes with ethanol, with ethoxide, and with hydrogen halides have been studied. I.r. (4000–80 cm.–1), n.m.r., and mass spectra are reported.
配合物卤代环戊二烯二喹啉-8-羟基金属(IV), C5H5MXox2(M = Ti, Zr;用喹啉-8-醇(oxH)和二卤代烃(环戊二烯基)金属(IV)[(C5H5)2MX2]在室温下在乙腈溶液中直接相互作用制备了X = Cl, Br和M = Hf, X = Cl)。研究了这些配合物与乙醇、乙醇和卤化氢的反应。报告了I.r (4000-80 cm - 1)、n.m.r和质谱。
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引用次数: 10
Photochemistry of tocoquinone-1 toco醌-1的光化学性质
Pub Date : 1971-01-01 DOI: 10.1039/J19710002248
G. Leary
The photochemistry of tocoquinone-1 has been investigated by use of steady-state and flash photolysis techniques. In polar solvents proton transfer leads to a long-lived transient assigned to an ortho-quinone methide. The photochemical behaviour of tocoquinone-1 is compared with that of vitamin K1.
采用稳态光解和闪光光解技术研究了toco醌-1的光化学反应。在极性溶剂中质子转移导致一个长寿命的瞬态分配给对醌的方法。将toco醌-1的光化学行为与维生素K1进行了比较。
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引用次数: 8
Binuclear mixed-metal complexes formed by nickel(II) and other 3d bivalent ions with tripod ligands 由镍(II)和其他三维二价离子与三脚架配体形成的双核混合金属配合物
Pub Date : 1971-01-01 DOI: 10.1039/J19710003686
M. Bacci, R. Morassi, L. Sacconi
Reaction of the five-co-ordinate [Ni(NP3)X]X complexes [NP3= tris(2-diphenylphosphinoethyl)amine; X = Cl, Br, I] with MX2 salts (M = Fe, Co, Ni, Zn) gives complexes of general formula NiM(NP3)X4. Spectrophotometric, conductometric, and far-i.r. data suggest for these complexes a binuclear non-ionic structure consisting of a square-planar ‘core’ with a NiNP2X chromophore, and a pseudo-tetrahedral ‘core’ with a MPX3 chromophore. The analogous nickel–manganese complexes undergo selective oxidation with formation of a phosphine oxide, probably bonded to MnII.
五配位[Ni(NP3)X]X配合物[NP3=三(2-二苯基膦乙基)胺的反应X = Cl, Br, I]与MX2盐(M = Fe, Co, Ni, Zn)配合得到通式NiM(NP3)X4。分光光度法、电导法和远红外法。数据表明,这些配合物的双核非离子结构由一个带有NiNP2X生色团的方形平面“核”和一个带有MPX3生色团的伪四面体“核”组成。类似的镍锰配合物经过选择性氧化形成氧化膦,可能与MnII结合。
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引用次数: 1
期刊
Journal of The Chemical Society A: Inorganic, Physical, Theoretical
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