Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.     

Mannich bases as model compounds for intramolecular hydrogen bonding I. Solid state structures and molecular calculations

Summary A survey of the structures and the properties of the hydrogen bonds inortho-aminomethylphenols and -naphthols in the solid state is presented. The results are compared with molecular structure calculations. The solid state complexes can exist in the molecular or in zwitterionic form. In the last case, only intermolecular hydrogen bonds forming cyclic dimers or linear chains were detected.

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Mannich-Basen als Modelle für Intramolekulare Wasserstoffbrücken, 1. Mitt. Festkörperstrukturen und Molekülrechnungen

Zusammenfassung Eine Übersicht über Strukturen und Eigenschaften von Wasserstoffbrücken inortho-Aminomethylphenolen und -naphtholen wird präsentiert. Die Ergebnisse werden mit Molekülrechnungen verglichen. Im Festkörper existieren diese Verbindungen in neutraler oder in zwitterionischer Form. Für den zweiten Fall können nur intermolekulare Wasserstoffbrücken nachgewiesen werden, und zwar in Dimeren oder in linearen Ketten.

     

Kinetics of muonic hydrogen drift in axial symmetric geometry

The kinetics of muonic atoms of hydrogen isotopes in an axially symmetric trap is studied. The problem of the determination of the initial kinetic energy distribution of µp and µd atoms from time-of-flight spectra is discussed. The effects of the scattering of muonic atoms from gas and of the stopping distribution are evaluated. When the collision length is much larger than the target radius, the moments of the kinetic energy distribution are shown to be determined by the time-of-flight spectrum in a model-independent way.     

一维螺旋状3，6-哒嗪二甲酸镉(Ⅱ)配位聚合物的合成与结构

Using the ligand pyridazine-3，6-dicarboxylate (H₂pzdc)， a coordination polymer [Cd₂(pzdc)₂(H₂O)₄] was synthesized and characterized by elemental analysis， thermal analysis， IR and single-crystal X-ray diffraction. The complex crystallizes in the tetragonal system with space group I4₁/a. The crystallographic data are: a=1.470 6(4) nm， c=1.489 8(6) nm， V=3.222 0(19) nm³， Z=16， μ=2.725 mm^-1， D_c=2.594 g·cm^-3， R₁=0.017 8， wR₂=0.044 6. In the complex， the cadmium(Ⅱ) ions with the eight-coordinated dodecahedral geometry are linked by the pzdc ligands to generate one-dimensional chains， which are associated into the three-dimensional architecture via O-H…O hydrogen bonding. CCDC: 658853.     

过渡金属钼钒砷杂多化合物的合成与TPR,TPD研究

Seven transition metal molybdovanadoarsenic heteropoly compounds have been synthesized and characterized using IR, UV, TG-DTA, pH potential titration techniques. The molecular formulae of these compounds are pro-posed to be H_xM_yAsMO₁₀V₂O₄₀·zH₂O(x=1～3, y=1,2, M=Cr, Mn, Fe, Co, Ni, Cu, Zn).They are all keggin structure. Surface nature of these compounds have been investigated by temperature programmed desorption and temperature programmed reduction techniques. NH₃-TPD results show that in TPD profiles of the compounds there are two desorption peaks corresponding to weak acid sites of desorption, respectively. Desorbing activativon energy and preexponential factor of weak acid site of desorption for compounds have been calculated. H₂-TPR re-sults show that introducting transtion metal to molybdovanarsenic acid, the reduction peak temperatures of H₂-TPR shift regularly with increasing d electron numbers of transition metals. In addition, Zn and Cu heteropoly com-pounds have yet apparent effect of hydrogen spill over.     

Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

二(邻香草醛缩丙醇胺)异硫氰酸根合锰(Ⅲ)的合成与晶体结构

本文报道了一个新配合物—二(邻香草醛缩丙醇胺根)异硫氰酸根合锰(Ⅲ)的合成及其晶体结构。配合物属于单斜晶系，空间群为P2₁/c，晶胞参数为：a=8.565(1), b=21.814(2), c=12.787(2)?, β=92.80(1)°。锰为六配位，在两个邻香草醛缩丙醇胺Schiff碱配体中，一个为三齿配体，另一个为双齿配体。NCS^-离子以N在轴向上与锰发生配位，由于Jahn-Teller效应，其键长为2.193?。另外晶胞中存在着罕见的H……S-C≡N氢键。     

碲氢化钠与胺烷基化苯并三氮唑的反应

碲氢化钠是一个用途广泛的磁试剂,自作为有用的去溴试剂以来,日益受到化学工作者的关注,不断有文献报道它的合成及应用.例如能有效地还原卤代烃、硝基化合物、叠氮化合物和亚胺等.近年来,Katritzky报道了胺烷基化苯并三氮唑衍生物的合成及应用,此衍生物中的苯并三氮唑基是很好的离去基团,易被各种亲核试剂所取代.我们在前文中对硒氢化钠与胺烷基化苯并三氮唑反应生成二苄基二硒醚的合成进行了报道.本文用碲氢化钠与胺烷基化苯并三氮唑反应,结果生成还原产物N-取代胺.