Syntheses and crystal structures of supramolecular compounds of tetranuclear ZrIV and HfIV aqua hydroxo complexes with macrocyclic cavitand cucurbituril

Slow evaporation of hydrochloric acid solutions of zirconium(iv) or hafnium(iv) oxochlorides and cucurbituril in air afforded compounds with composition [M₄(OH)₈(H₂O)₁₆]Cl₈·(C₃₆H₃₆N₂₄O₁₂)·16H₂O, where M = Zr (1) or Hf (2). According to the X-ray diffraction data, complexes 1 and 2 are isostructural. Their crystal structures can be described as packings of polymer chains consisting of alternating cucurbituril molecules and tetranuclear cations [M₄(OH)₈(H₂O)₁₆]⁸⁺ linked to each other via an extensive network of hydrogen bonds. Compound 2 is the first structurally characterized tetranuclear hafnium aqua complex.     

Synthesis and characterization of a novel tantalum chalcogen-rich molecular cluster with square planar metal core

Black single crystals of Ta(4)Se(9)I(8) are obtained in a high yield by heating Ta, Se, and I(2) at 300 degrees C in 1:2.2:1.0 molar ratio. In the structure, the tantalum atoms form a square, with four Se(2) ligands bridging the Ta-Ta edges and one capping the square. Each Ta atom has two terminal iodine atoms. The compound is diamagnetic and has only two electrons for metal-metal bonding.     

Synthesis of polyrotaxanes based on α-cyclodextrin and poly(ethylene oxide)

Inclusion complexes of poly(ethylene oxide) with α-cyclodextrin are the key compounds in the synthesis of polyrotaxanes. These complexes prepared in aqueous solutions contain free cyclodextrin, which cocrystallizes with the major reaction product. These complexes dissociate upon dissolution in DMF and DMSO to form cyclodextrin and pseudopolyrotaxanes with a low cyclodextrin content. Polyrotaxane was synthesized with the use of poly(ethylene oxide)-α,ω-bis-amine as a linear component. The end-groups of the polymer in the inclusion complex were modified by the reaction with 2,4-dinitrofluorobenzene. A procedure was developed for purification of a polyrotaxane with high cyclodextrin content. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1914–1918, August, 2005.     

Potential function of internal rotation of (CH3)2CClNO,CH3CCl2NO,and their deuterium analogs

The potential function has been constructed for internal rotation of the NO-group in (CH₃)₂CClNO, CH₃CCl₂NO, and their deuterium analogs. It has been established that the N=O bond in the cis_Cl conformer of CH₃CCl₂NO does not eclipse the C-Cl bond, rather forming an angle of approximately 30. It has been shown that a change in substitutent on the -carbon atom may produce a substantial change in the form of the potential function of internal rotation (PFIR) of the NO group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 550–555, March, 1990.     

ESR spectra of products of oxidation of endometallofullerenes M@C82 (M = Y,La, Ce,Gd)

The ESR spectra of the products of oxidation of solutions and powders of Y@C₈₂ and La@C₈₂ with fuming sulfuric acid were studied. Based on the oxidation conditions and the sequence of spectral patterns, the spectra were attributed to the radical cations M@C₈₂ ⁿ⁺ (n = 2, 4), dimers M³⁺ ₂@C₁₆₄ ⁺, and polyendometallofullerenes.     

Molecular and crystalline structure of the enol form of (dimorpholinophosphoryl)chloroacetaldehyde and (dimorpholinophosphoryl)-dibromomethane

The crystal and molecular structures of the products of the halogenation of the dimorpholide of ethoxyvinylphosphonic acid were determined by the method of x-ray structure analysis. It was established that (dimorpholinophosphoryl)chloroacetaldehyde only exists in the crystals as the Z-enol [(Z)-1-hydroxy-2-(dimorpholinophosphoryl)-2-chloroethene] with intra- and intermolecular H-bonds (=CH...O=P and OH...O=P). The (dimorpholinophosphoryl)dibromomethane forms centrosymmetric eight-membered cyclic dimers in the crystals due to intermolecular CH...O=P H-bonds. The structure of the morpholine and phosphoryl groups in both compounds was discussed.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2730–2737, December, 1992.     

Inclusion of nickel(<Emphasis Type="SmallCaps">II</Emphasis>) and copper(<Emphasis Type="SmallCaps">II</Emphasis>) complexes with aliphatic polyamines in cucurbit[8]uril

The inclusion compound of macrocyclic cavitand cucurbit[8]uril (CB[8]) with the nickel(II) complex containing the tetraazamacrocyclic ligand cyclam, {[Ni(cyclam)]@CB[8]}Cl₂··16H₂O (1), and the inclusion compounds of CB[8] with the copper(II) bis-ethylene-diamine complex, {trans-[Cu(en)₂(H₂O)₂]@CB[8]}Cl₂·{CB[8]}·42H₂O (2a) and {trans-[Cu(en)₂(H₂O)₂]@CB[8]}Cl₂·17H₂O (2b), were synthesized and characterized by X-ray diffraction analysis, IR and ESR spectroscopy, and electrospray mass spectrometry. Guest—host inclusion compounds can be directly synthesized starting from a metal complex and cucurbit[8]uril, as was exemplified by the preparation of compounds 2a and 2b.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2414–2419, November, 2004.     

Optically active organometallic compounds (a personal account from the inside)

Results of a long experience of our group in Moscow in the area of chiral organometallic stereochemistry are described. They embrace optically active organometallic derivatives of mercury, palladium, platinum, functionalized ferrocenes, ruthenocenes, and cymantrenes as well as less common objects such as organometallic fullerenes and the cyclodextrin-metallocenes inclusion complexes.