Synthesis of nonequilibrium Ir<Subscript>x</Subscript>Re<Subscript>1-x</Subscript> solid solutions. Crystal structure of [Ir(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl]<Subscript>2</Subscript>[ReCl<Subscript>6</Subscript>]Cl<Subscript>2</Subscript>

Synthesis of five binary complex salts with an [Ir(NH₃)₅Cl]²⁺ complex cation is described. The counterions are [ReCl₆]^2–, [IrCl₆]^2–, [ReBr₆]^2–, and Cl^–. A polycrystal X-ray diffraction study has been performed for [Ir(NH₃)₅Cl]₂[ReCl₆]Cl₂, and its crystal structure has been determined. A series of Ir _x Re_1–x phases (0.5 x > 1) were obtained by reductive thermolysis. For the Ir-Re system, the history of the V/Z(x) dependence has been refined.Original Russian Text Copyright © 2004 by S. A. Gromilov, S. V. Korenev, I. V. Korolkov, K. V. Yusenko, and I. A. BaidinaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 508–515, May–June 2004.     

Synthesis of polyacetylene with titanocene-aluminum hydride catalysts

Heterometallic hydride titanocene-aluminum complexes Cp₂Ti(-H)₂AlH(X) and (Cp₂Ti)₂AlH₄X are highly efficient homogeneous catalysts for acetylene polymerization. The binuclear complex of the composition Cp₂Ti(-H)₂AlH₂ at 2.2–3.2M concentrations in ether-toluene solutions exhibits the maximum activity in this reaction. It is believed that the mechanisms of the isomerization of olefins and the polymerization of acetylene are similar and, correspondingly, the compositions and structures of the active sites in both processes are close to each other. The polyacetylene formed with hydride catalysts (mostly thecis-isomer) after doping with iodine has an electrical conductivity of 1.5–2.0 · 10⁴ Ohm^–1 cm^–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 405–409, March, 1994.The work was carried out with the financial support of the Russian Foundation for Basic Research, project No. 93-03-5757.     

Apparent molal volumes and adiabatic compressibilities of ethylene glycol derivatives in water at 5, 25, and 45°C

Density and ultrasonic velocity measurements were made on a series of dilute equeous solutions of H(OCH ₂ CH ₂ )_nOH, CH ₃ (OCH ₂ CH ₂ )_nOCH ₃ , H(CH ₂ )_nOCH ₂ CH ₂ OH (n=1–4), and poly(ethylene glycol) at 5, 25, and 45°C. The additivity of the limiting partial molal volumes ( ) and adiabatic compressibilities ( ) for CH ₂ and CH ₂ CH ₂ O groups was tested by using the observed and values of the solutes. The and values of the CH ₃ , CH ₂ , CH ₂ CH ₂ O, and CH ₂ OH groups were estimated and discussed in relation to hydration effects. The and values of alkoxyethanols calculated on the basis of the additivity of the group partial molal quantities were in good agreement with the observed values. The behavior of the limiting partial molal isothermal compressibility of alkoxyethanols was similar to that of the adiabatic compressibility.     

Half-lanthanidocenes catalysts via the “borohydride/alkyl” route: A simple approach of ligand screening for the controlled polymerization of styrene

The “borohydride/alkyl” (B/A) route initially reported for isoprene has been applied successfully to the polymerization of styrene. This method provides via an in situ approach an interesting tool for the assessment of the influence of a ligand on the performance of half-lanthanidocene catalysts. All systems lead to well-controlled oligomerization/polymerization processes. This method is thus a convenient tool for the controlled polymerization of styrene starting from a common trisborohydride precursor and commercial ligands. The influence of the nature of several ligands on the activity could be established, with trends corresponding to those obtained starting from the isolated precursors: HCpHCp^Ph₃>HCp^*(Cp=C₅H₅,Cp^Ph₃=1,2,4-Ph₃C₅H₂,Cp^*=C₅Me₅). These results suggest an influence of the electron donating ability of the ligand rather than steric requirements.     

Oxidation of aromatic compounds: XII. Regio- and stereoselective oxidative dimerization of alkyl 3-arylpropynoates in the system CF<Subscript>3</Subscript>CO<Subscript>2</Subscript>H-CH<Subscript>2</Subscript>Cl<Subscript>2</Subscript>-PbO<Subscript>2</Subscript>

Regio- and stereoselective oxidative dimerization of alkyl 3-arylpropynoates in the system CF₃CO₂H-CH₂Cl₂-PbO₂ (1–30 h, 0–20°C) leads to dialkyl (E)-2,3-bis(arylcarbonyl)-2-butene-1,4-dioates with trans arrangement of the substituents at the double bond.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1329–1333.Original Russian Text Copyright © 2004 by Savechenkov, Vasilev, Rudenko.For communication XI, see [1].     

Synthesis and characterization of η<Superscript>3</Superscript>-allyl palladium(II) complexes with Ph<Subscript>2</Subscript>P(S)CHP(S)Ph<Subscript>2</Subscript> and OC(CF<Subscript>3</Subscript>)CHCO(C<Subscript>4</Subscript>H<Subscript>3</Subscript>S) co-ligands

The new complexes [(η³-Me₂CCMeCH₂)Pd{η²-Ph₂P(S)CHP(S)Ph₂] (1), [(η³-Me₂CCMeCH₂)Pd{η²-OC(CF₃) CHCO(C₄H₃S)}] (2) and [(η³-CH₂CMeCH₂)Pd{η²-OC(CF₃)CHCO(C₄H₃S)}] (3) have been synthesized by reacting [(η³-allyl)Pd(μ-Cl)]₂ with Ph₂P(S)CH₂P(S)Ph₂ and OC(CF₃)CH₂CO(C₄H₃S) in the presence of base. All have been characterized by elemental analysis, FT-IR, ¹H-n.m.r and FAB-mass spectroscopy. Spectroscopic studies suggest that both ligands are bidentate, forming six-membered Pd-S-P-C-P-S and Pd-O-C-C-C-O palladacycles, the η³-allyl group completing the coordination sphere.     

Molecular and crystal structures of Ph2P(O)(CH2)2OH and Ph2P(O)CH2(C6H6)OH

The molecular and crystal structures of Ph₂P(O)(CH₂)₂OH and Ph₂P(O)CH₂(C₆H₆)OH have been determined. For the first compound the space group is with unit cell dimensions a=10.505(2), b=13.720(2), c=14.782(3) Å; =72.58(6), =76.95(6), =72.49(6)° for Z=6 (Syntex diffractometer,MoK radiation, 2996 reflections, R=3.2%). The second compound crystallizes in the space group P2₁2₁2₁ with unit cell dimensions a=9.371(3), b=9.014(3), c=18.461(5) Å for Z=4 (DAR-UM diffractometer,CuK radiation, 909 reflections, R=4.9%). In Ph₂P(O)(CH₂)₂OH, three independent molecules differing in structural details are linked by the P=O...O hydrogen bonds (O...H is 1.84, 1.80, and 1.86 Å), to form a chain. In Ph₂P(O)CH₂(C₆H₆)OH, the molecules are joined by pairs of the P=O...H–O bonds (O...H is 1.81 Å) to form 16-membered dimeric associates.Institute of Chemical Physics, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 109–118, May–June 1993.Translated by T. Yudanova     

Structural flexibility of the (η<Superscript>3</Superscript>-allyl)· Palladium complex with sorbic acid

The density functional theory method was used to study the structural flexibility of a hydroxyl-containing (³-allyl)palladium complex with sorbic acid [(³-C₃H₃(CH(OH)CH₃)(COOH))PdCl₂]^– and its analog [(³-C₃H₃(CH(OH)CH₃)(COO))PdCl₂]^2–. Potential surfaces of internal rotation in the CH(OH)CH₃ substituent at the terminal carbon atom of the allyl fragment have been constructed for the complexes. It is found that weak hydrogen bonds COOH...Cl and OH...Cl are formed in the molecules. Various types of structural deformation of the complex are discussed.Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 435–441, May–June, 2004.Original Russian Text Copyright © 2004 by T. A. Morozova, A. P. Belov, and A. V. Krylov     

Syntheses and spectra of chromium-titanium complexes bridged by carboxylate substituted cyclopentadienyl group: The structure of Cp2Ti(CH3){[OC(O)C5H4]Cr(NO)2Cl}

Mono-demethylation of Cp₂Ti(CH₃)₂ in dichloromethane with 1 M equivalent of [η⁵-(C₅H₄COOH)]Cr(CO)₂NO (5), [η⁵-(C₅H₄COOH)]Cr(NO)₂X] (X = Cl 6, X = I 7) and [η⁵-(C₅H₄COOH)]W(CO)₃CH₃ (8) gives Cp₂Ti(CH₃){[OC(O)C₅H₄]Cr(CO)₂NO} (9), Cp₂Ti(CH₃){[OC(O)C₅H₄]Cr(NO)₂Cl} (10), Cp₂Ti(CH₃){[OC(O)C₅H₄]Cr(NO)₂I} (11) and Cp₂Ti(CH₃){[OC(O)C₅H₄]W(CO)₃CH₃} (12), respectively. The structure of 10 has been solved by X-ray diffraction studies. One of the nitrosyl groups is located at the site away from the exocyclic carbonyl carbon of the Cp(Cr) ring with twist angle of 178.1°. All the data reveals that Cp₂Ti(CH₃)- is a strong electron-donating group. The opposite correlation was observed on the chemical shift assignments of C(2)-C(5) in compounds 5-12, using HetCOR NMR spectroscopy, as compared with the NMR data of their ferrocene analogues. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of ¹³C NMR data and those of 10 are compared with the calculations via density functional B3LYP correlation- exchange method.     

Reaktionen mit phosphororganischen Verbindungen, 17. Mitt.: Zur Oxydation von β-Oxophosphoniumrhodaniden mit Bleitetraacetat

Zusammenfassung Die Oxydation von Phosphoniumrhodaniden (C₆H₅)₃P–CH (Alkyl) CO–CHR₁R₂ SCN mitPbTA liefert in Abhängigkeit von den Resten R₁ und R₂ Verbindungen des Typs R₁R₂C=C=C (SCN) (Alkyl) und die daraus durch 1,3-Umlagerung resultierenden Senföle R₁R₂C(NCS)–CC-Alkyl. Für R₁=R₂=H und R₁=Cl, R₂=C₂H₅ entsteht fast nur die Allenverbindung. Für R₁=H und R₂=Alkyl isoliert man ein Gemisch aus Allenrhodanid und Acetylenverbindung. Wenn R₁=R₂=(–CH₂–CH₂–CH₂–) oder CH₃ darstellen, kommt es zur ausschließlichen Bildung des Acetylensenföls.Aus -Methoxyphosphoniumrhodaniden (C₆H₅)₃P–CH (OCH₃)CH–CHR₁R₂ SCN erhält man bei der Umsetzung mitPbTA R₁R₂CH–CO–CH(OCH₃) (NCS) und R₁R₂CH–CO–CH(OCH₃) (S–CO–CH₃).

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The oxidation of phosphoniumrhodanides (C₆H₅)₃P–CH (Alkyl)CO–CHR₁R₂ SCN with lead tetraacetate results in the formation of R₁R₂C=C=C=(SCN) (alkyl) type compounds, dependent on the substituents R₁ and R₂ sometimes followed by a 1,3-rearrangement to mustard oils R₁R₂C(NCS)–CC–alkyl. The case R₁=R₂=H and R₁=Cl, R₂=C₂H₅ yields almost exclusively the allenic compound. With R₁=H and R₂-alkyla mixture of allene rhodanide and the acetylenic compound is isolated. If R₁ and R₂ stand for –CH₂–CH₂CH₂– or CH₃, only the mustard oil with an acetylenic group is produced.Upon the oxidation of (C₆H₅)₃P–CH(OCH₃)CO–CHR₁R₂ SCN^– we observed formation of R₁R₂CH–CO–CH(OCH₃) (NCS) and R₁R₂CH–CO–CH(OCH₃) (S–CO–CH₃).

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Mit 5 Abbildungen

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Herrn Prof. Dr.L. Schmid zum 70. Geburtstag gewidmet.

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16. Mitt.:Elisabeth Werner undE. Zbiral, Angew. Chem.79, 899 (1967).     

Vibrational spectroscopic study of the structure of Ti(III) organometallic compounds

Conclusions A full interpretation was carried out for the vibrational spectra of TiR₃, where R= -CH₂C₆H₅, -CH₂C(CH₃)₂C₆H₅, and-CH₂Si(CH₃)₃. The absorption bands for the Ti-C bonds were delineated. A dimeric structure was established for the compounds studied with a Ti-Ti bond, whose band lies at 230–280 cm^–1. There is an interaction of the titanium atom with the -carbon atom of the ligand for the Ti(III) benzyl and neophyl derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2736–2739, December, 1987.     

PMR spectra of sulfur-containing 1-organylsilatranes

Conclusions The¹H chemical shifts of sulfur-containing 1-organylsilatranes of type YCH₂Si(OCH₂-CH₂)₃N, where Y RS, RS(O), and of sulfonium salts of the silatrane series of type [YCH₂Si-(OCH₂CH₂)₃N]I^–, where Y = RRS⁺, are determined by the valence state of the sulfur atom and the steric stresses. The molecular conformation of the studied compounds was established.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 464–467, February, 1979.     

An ab initio study of the electronic and steric structure of Cl<Subscript>2</Subscript>ZX molecules (Z = P and As)

The electronic and steric structure of the Cl₂ZX molecules [Z = P and As, X = C₂H₅, N(CH₃)₂, and OCH₃] was examined by RHF/6-31G(d) and MP2/6-31G(d) calculations. The data on the electron distribution at the Cl atoms are compared with the published ³⁵Cl NQR data. The main reason for a decrease in the NQR frequency of the molecules with X = N(CH₃)₂ and OCH₃ as compared to the ethyl-substituted compounds is an increase in the population of the 3p components of their p _z(p _σ) orbitals. With X = N(CH₃)₂, electron distribution at two Cl atoms differs significantly.     

Structure and some properties of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>{CH<Subscript>3</Subscript>CON(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

A new complex [UO₂CrO₄{CH₃CON(CH₃)₂}₂] (I) was studied by thermal analysis, IR spectroscopy, and X-ray crystallography. The crystals are monoclinic: a = 13.8108(11) Å, b = 8.6804(7) Å, c = 13.0989(10) Å, β = 104.777(1)°, V = 1518.4(2) ų, space group P2₁/c, Z = 4, R = 2.39%. The structure of I contains infinite chains of the [UO₂CrO₄{CH₃CON(CH₃)₂}₂] composition running along [001]; the complex belongs to the AT¹¹M¹ ₂ crystal-chemical group (A = UO ₂ ²⁺ , T¹¹ = CrO ₄ ^2? , M¹ = CH₃CON(CH₃)₂) of uranyl complexes. The chains are linked into a three-dimensional framework due to hydrogen bonds between oxygen atoms of chromate ions and hydrogen atoms of methyl groups of the dimethylacetamide.     

Radical addition of alkylbenzenes to α,α-dichlorovinyl compounds

Conclusions Toluene and p-xylene react with ,-dichloroolefins CCl₂=CHCH₂R (R = Cl, OCH₃, CH₂CH₃, and CH₂-CH₂ Cl) with tert-butyl peroxide initiation, to form adducts predominantly with the structure HCCl₂CH(CH₂C₆H₄X)-CH₂ R (X =p–CH₃), which corresponds to the orientation of the addition of the benzyl radicals to the -carbon atom of the chloroolefin with the formation of the more stable radicals. The formation of compounds CCl₂ = CHCH(CH₂C₆H₅)CH₂CH₂Y (Y = H and Cl) was also noted.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1809–1812, August, 1976.     

Crystal structure of Ba(VUO<Subscript>6</Subscript>)<Subscript>2</Subscript>

The crystal structure of Ba(VUO₆)₂ was determined by X-ray diffraction at 243 K: monoclinic crystal system, space group P2₁/c, unit cell parameters a=6.4992(6) Å, b=8.3803(8) Å, c=10.4235(9) Å, =104.749(2) °, Z=2. The structure contains close-packed [VUO₆] ₂ ^- layers formed by the dimers of the flattened U₂O₁₂ pentagonal bipyramids and by the dimers of V₂O₈ square pyramids. The neighboring layers are bound by the statistically distributed barium atoms.Original Russian Text Copyright © 2004 by E. V. Alekseev, E. V. Suleimanov, E. V. Chuprunov, and G. K. FukinTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 544–548, May–June 2004.     

Aromatic derivatives of 2H-pyrimidino[5,6-b]-1,4-thiazine

5-R¹3-(4-R-Phenyl)-2H-pyrimidino[5,6-b]-1,4-thiazines [R¹=N(CH₃)₂ or OCH₃], which exist primarily in the 2H form, were synthesized by the reaction of -bromoacetophenones with 4-R¹-5-amino-6-thiopyrimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 275–277, February, 1987     

Magneto-optic and luminescent properties of tellurite glass TeO<Subscript>2</Subscript>-ZnCl<Subscript>2</Subscript> doped with rare-earth elements

Tellurite glasses were synthesized on the basis of the binary system composed of 70 mol % TeO₂ and 30 mol % ZnCl₂ and doped with Nd³⁺, Pr³⁺, Tb³⁺, Er³⁺, Yb³⁺, Ho³⁺. The physicochemical, luminescent, and magneto-optic properties of these glasses were studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1262–1265.Original Russian Text Copyright © 2004 by Grishin, Gurev, Intyushin, Elliev, Pavlova, Savikin.     

Synthesis of heterobimetallic lanthanide <Emphasis Type="Italic">tert</Emphasis>-butoxides and their catalytic properties in reactions of CO<Subscript>2</Subscript> with epoxides

Heterobimetallic tert-butoxides (t-BuO)₅Cu₂Ln (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), (t-BuO)₅MLa (M = Mn, Fe, Co, Ni), (t-BuO)₅ZnNd, and (t-BuO)₄ZnFe were prepared in high yields by the reaction of t-BuOLi with a stoichiometric mixture of a lanthanide halide LnX₃ (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; X = Cl, I) and a d-transition metal salt MX_n (M = Zn, Cu, Mn, Fe, Co, Ni; X = Cl, Br). (t-BuO)₅Cu₂Ln (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) and (t-BuO)₅ZnNd at room temperature and atmospheric pressure induce copolymerization of CO₂ with cyclohexene oxide, affording the polycarbonate in a yield of 3–6 g g^–1 catalyst. The complex (t-BuO)₅FeLa, and also iron alcoholates (t-BuO)₂Fe and (t-BuO)2_Fe(bipy) under similar conditions catalyze the reaction of CO₂ with propylene oxide affording monomeric propylene carbonate in a yield of 35–45 g g^–1 catalyst.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1295–1299.Original Russian Text Copyright © 2004 by Nikitinskii, L. Bochkarev, Khorshev, M. Bochkarev.This revised version was published online in April 2005 with a corrected cover date.     

Sila-Riechstoffe und Riechstoff-Isostere VII: Reaktionen und Derivate der Benzyldialkylphosphinimide

Zusammenfassung Derivatives of benzyldialkylphosphinimides C₆H₅CH₂-PRR=NH (C) with =NCH₃, =NSiMe ₃, =O, =S, –CS ₂ and –NH₂]NCS instead of =NH groups (compare Scheme 1) were prepared and characterized. They neither show the H/D exchange of CH₂ benzyl protons with CDCl₃ nor the thermal formation of stilbene on heating like the parent compounds C, but they give in the case of =NCH₃ and =NSiMe ₃ analogously aHorner-Wittig reaction with aldehydes. CS₂ reacts with C under NH/S-exchange. The quality of smell ofPhCH₂-PRR =NCH₃ (none, later fishy) is quite different from that of isostericPhCH₂-SiRR –OCH₃ (flowery-honeylike/minty) and the smell of C (metallic/chlorinated hydrocarbon-like) from that ofGrimm hydride isostersPhCH₂–PRR=O (weak; flowery-waxy). The theory ofAmoore (size and shape of molecules control their smell qualities) must be called in question.

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Sila-perfumes and isosteric perfumes, VII: Reactions and derivatives of benzyldialkylphosphinimides