Metallsubstituierte Phosphaalkene und Acylphosphane. 31. Zur Reaktivität von (η5-C5Me5)(CO)2FeP = C(NMe2)2 gegenüber Zinndichlorid. Röntgenstrukturanalyse von {(η5-C5Me5)[η1-(Me2N)2C = P?P = C(NMe2)2](CO)2Fe}+{[Me2N)2C]2P}+(FeCl4)2−

Transition-Metal Substituted Phosphaalkenes and Acyl Phosphanes. 31 [1] Reactivity of (η⁵-C₅Me₅)(CO)₂FeP = C(NMe₂)₂ towards Tin Dichloride. X-Ray Structure Analysis of {(η⁵-C₅Me₅)[η¹-(Me₂N)₂C = P? P = C(NMe₂)₂](CO)₂Fe}⁺{[Me₂N)₂C]₂P}⁺(FeCl₄)^2? Reaction of metallophosphaalkene (η⁵-C₅Me₅)(CO)₂ · FeP = C(NMe₂)₂ ( 1 ) with anhydrous tin dichloride affords the salt-like compound {(η⁵-C₅Me₅)[η¹-(Me₂N)₂C = P? P = C(NMe₂)₂] · (CO)₂Fe}⁺{[(Me₂N)₂C]₂P}⁺(FeCl₄)^2? 5 which is characterized by single crystal X-ray analysis and spectra (IR, ¹H, ³¹P-NMR).     

Equilibria in aqueous cadmium-chloroacetate-glycinate systems. A convolution-deconvolution cyclic voltammetric study

Summary Stability constants and composition of cadmium-glycinate binary complexes were determined using cyclic voltammetry. Furthermore, binary and ternary complex equilibria for chloroacetates and glycinate with cadmium in 0.1M aqueous KNO₃ atpH 10.4 and 298 K were investigated. Cadmium forms binary complexes with chloroacetates of low stability and ternary ones with chloroacetate-glycinate of significant stability.

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Gleichgewichte in wäßrigen Cadmium-Chloroacetat-Glycinat-Systemen. Untersuchungen mittels zyklischer Voltammetrie

Zusammenfassung Gleichgewichtskonstanten und Zusammensetzung binärer Cadmium-Glycinat-Komplexe wurden mittels zyklischer Voltammetrie bestimmt. Weiters wurden binäre und ternäre Gleichgewichte von Chloroacetaten und Glycinat mit Cadmium in 0.1M KNO₃ beipH 10.4 und 298 K untersucht. Cadmium bildet binäre Komplexe geringer Stabilität mit Chloroacetaten und ternäre Komplexe von beträchtlicher Stabilität mit Chloroacetaten und Glycinat.

     

镧系元素双1：11系列杂多蓝的红外光谱和紫外光谱研究

本文首次系统研究了镧系元素钼采双１：１１系列两子杂多蓝ＫｚＨｙ（Ｌｎ（ＸＭｏ１１Ｏ３９０２）．ｎＨ２Ｏ（Ｘ＝Ｐ，Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ；Ｘ＝Ｓｉ，Ｌｎ＝Ｃｅ，Ｐｒ，Ｓｍ，Ｔｂ，Ｄｙ）的红外光谱和紫外光谱，对特征峰进行指认，并与还原前的杂多酸盐进行比较，发现有的特征峰出现小的位移，有的峰强度稍有变化，所以得出结论，还原前后，杂多阴离子结构基本不变，但有轻微的畸变。     

Neue Komplexe des Titans mit silylierten Aminoiminophosphoran- und Sulfodiimidliganden

New Complexes of Titanium with Silylated Aminoiminophosphorane and Sulfodiimide Ligands TiCl₄ forms a 1 : 1 adduct with S(NSiMe₃)₂ to give compound 1 and with Me₂S(NSiMe₃)₂ compound 2 , respectively. The reaction of TiCl₄ with Ph₂S(NSiMe₃)₂ yields the disubstituted compound Ph₂S(NTiCl₃)₂X₄THF 3 which crystallizes in space group P1 . Reaction of TiCl₄ with (Me₃Si)₂NPPh₂NPPh₂NSiMe₃ leads to an exchange of one silyl group with a TiCl₃ moiety. In this molecule the Ti-atom is only four-coordinated. The compound crystallizes in the space group P2₁/c. No chelate complexes are formed by reactions of CpTiCl₃, Cp*TiCl₃ and Cp*TiF₃ with Ph₂P(NSiMe₃)₂H, this is shown by X-ray structural analysis of Cp*TiCl₂NPPh₂NHSiMe₃ 6 . Crystals of 6 are obtained in space group P1 .     

Transport of monosaccharides through a liquid membrane mediated by lipophilic alkaline earth metal complexes

Lipophilic alkaline earth metal complexes, prepared from the corresponding metal hydroxides and phosphoric acid diesters, are quite effective for the transport of some monosaccharides, especially ribose, across a chloroform liquid membrane under neutral conditions.     

Kinetic Studies on Substitution Reactions of Carbonylmetal Complexes

Kinetic studies of substitution reactions of carbonylmetals and of carbonylmetal derivatives in which other ligands (n or π donors) besides CO are bound to the metal atom have recently attracted great interest, and the results of these investigations throw a new light on theoretical and preparative problems. The substitution mechanism is determined mainly by steric and electronic factors.     

Optical Activity from Asymmetric Transition Metal Atoms

The preparation and resolution of asymmetric organometallic compounds of the transition series with four different ligands on the metal atom are described. Some of the optically active complexes retain their configuration, while others undergo racemization in solution. Their properties and reactions are discussed. Centers of asymmetry at transition metal atoms can also be detected on the basis of the magnetic nonequivalence of diastereotopic groups. Information about the configurational stability of such compounds can be obtained by investigation of the temperature dependence of the nuclear magnetic resonance spectra.     

四水顺丁烯二酸镍配合物的光谱研究

四水顺丁烯二酸镍配合物晶体是由苹果酸和碳酸镍反应制得的。在这一体系中，加热时苹果酸转化为马来酸并与镍离子络合物成标题配合物。本文测定了该配合物的电子吸收光谱和光声光谱，并用配位场理论定地解释了其光谱性质，得到了配合物的晶场参数及中心离子的轨道能级。理论结果与实验结果的互洽表明了配合物晶体结构与电子结构的一致。     

Pyridine- and pyrimidine-2-thiolate complexes of ruthenium

A series of mononuclear ruthenium complexes containing pyridine- and pyrimidine-2-thiolato ligands was prepared and characterized. The new compounds of general formula CpRu(PPh₃)(κ²S,N-SR) (1) (SR = pyridine-2-thiolate (a), pyrimidine-2-thiolate (b)) were prepared directly by reacting the thiolato anions (RS⁻) with CpRu(PPh₃)₂Cl. Complexes 1 readily react with NOBF₄ or CO in THF at room temperature to give [CpRu(PPh₃)(NO)(κ¹S-HSR)][BF₄]₂ (2) and CpRu(PPh₃)(CO)(κ¹S-SR) (3), respectively. The one-pot reaction of CpRu(PPh₃)₂Cl, thiolato anions and bis(diphenylphosphino)ethane (dppe) gave CpRu(dppe)(κ¹S-SR) [dppe: Ph₂PCH₂CH₂PPh₂ (4)]. The complex salts, [CpRu(PPh₃)₂(κ¹S-HSR)]BPh₄ (5) are prepared by mixing CpRu(PPh₃)₂Cl, HSR and NaBPh₄ at room temperature. The structures of CpRu(PPh₃)(κ²S,N-Spy) (1a), [CpRu(PPh₃)(NO)(κ¹S-HSpy)][BF₄]₂ (2a) and CpRu(PPh₃)(CO)(κ¹S-Spy) (3a), (py = C₅H₄N) have been determined.