Lithiation of the Tin-containing Sulfone Me3SnCH2CH2CH2SO2C6H4CH3-4

The tin-containing sulfide Me₃Sn(CH₂)₃-S-C₆H₅CH₃-4 obtained by photoaddition of 4-toluene- thiol to allyltrimethyltin was oxidized with hydrogen peroxide to synthesize the tin-containing sulfone Me₃Sn(CH₂)₃-SO₂-C₆H₄CH₃-4, the tin and sulfur atoms in which are separated by a trimethylene bribge. Treatment of the sulfone with butyllithium gave a first tin-containing lithium salt having a red-brown color. The exchange reaction of this salt with methyl iodide resulted in formation of two new isomeric tin-containing sulfones Me₃SnCH₂CH₂CH(CH₃)-SO₂-C₆H₄CH₃ and Me₃Sn(CH₂)₃-SO₂-C₆H₄CH₂CH₃ identified by ^1HNMR spectroscopy. The latter result implies that the tin-containing sulfone is lithiated both by the methylene group adjacent to the sulfonyl group and by the toluene methyl group.     

Reaktionen von Uranpentabromid Die Kristallstrukturen von PPh4[UBr6], PPh4 [UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN und (PPh4)2[UO2Br4] · 2CH2Cl2

Reactions of Uranium Pentabromide. Crystal Structures of PPh₄[UBr₆], PPh₄[UBr₆] · 2CCl₄, (PPh₄)₂[UBr₆] · 4CH₃CN, and (PPh₄)₂[UO₂Br₄] · 2CH₂Cl₂ PPh₄[UBr₆] and PPh₄[UBr₆] · 2CCl₄ were obtained from UBr₅ · CH₃CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl₄. Their crystal structures were determined by X-ray diffraction. PPh₄[UBr₆]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh₄[UBr₆] · 2CCl₄: 2973 reflexions, R = 0.074, space group P2₁/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr₅ with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr₄ · CH₃CN and UBr₄ · 3CH₃CN, respectively. These react with PPh₄Br in acetonitrile affording (PPh₄)₂[UBr₆] · 4CH₃CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P2₁/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt₄)₂[U₂Br₁₀] was obtained; (PPh₄)₂[U₂Br₁₀] formed from UBr₄ and PPh₄Br in CH₂Cl₂. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh₄)₂[U0₂Br₄]· 2 CH₂Cl₂, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr₆-, 276.7 pm for UBr₆^2? and 282.5 pm for UO₂Br₄^2?     

AsPh4[W2Cl4(N3S2)3] · CCl4; Synthese und Kristallstruktur

AsPh₄[W₂Cl₄(N₃S₂)₃] · CCl₄; Synthesis and Crystal Structure The title compound was obtained in form of black crystals along with other products by the reaction of H₂S and AsPh₄[WCl₄(N₃S₂)] in dichloromethane and subsequent addition of CCl₄. Its crystal structure was determined by X-ray diffraction (3036 observed reflexions, R = 0.051). Crystal data: triclinic, space group P¯1, Z = 2, a = 1369, b = 1398, c = 1441 pm, α = 64.8, β = 68.02 and γ = 58.1°. The compound consists of AsPh₄^⊕ ions, CCl₄ molecules and [W₂Cl₄(N₃S₂)₃]^? ions. In the latter, one tungsten atom is member of one planar WN₃S₂ ring while the second tungsten atom belongs to two such rings forming a nearly planar S₂N₃WN₃S₂ unit. Two nitrogen atoms of this unit are linked to the other tungsten atom forming a WN₂W ring. Two chloro ligands at each tungsten atom complete the coordination sphere to coordination numbers of six.     

Über cyclische tertiäre Arsine und sekundäre Arsenoxide

α,ω-Alkane-bis-diphenylarsines and -dimethylarsines, R₂AsC_nH_2nAsR₂, may be obtained from dichloroalkanes and sodium diorganyl-arsenides, R₂AsNa. The latter are prepared from tetraphenyl- and tetramethyl-diarsenic-sulphide, respectively, (R₂As)₂S. Elemental sodium eliminates on each As atom of the tetraphenyl-diarseno-alkanes one phenyl group, and on oxidation α,ω-alkane-diphenylarsenic acids are obtained. Reduction of these acids by means of SO₂ yields cyclic, secondary arsenic oxides, whereas H₃PO₂ gives cyclic arsines with As ? As bonds. Disodium-phenylarsenide, C₆H₅AsNa₂, prepared from (C₆H₅AsS)₄, reacts with longer dichloroalkanes to form cyclic tertiary phenylarsines which may contain, in addition to As, further heteroatoms such as N, O or S. Those arsines, which only contain carbon as the ring atoms, commutate with AsCl₃ to 1-chloro-arsolane and 1-chloroarsenane.     

Neue Nitrosylkomplexe des Rheniums: ReCl3(NO)2, ReCl3(NO)2(CH3CN), AsPh4[ReCl4(NO)2]

New Nitrosyl Complexes of Rhenium: ReCl₃(NO)₂, ReCl₃(NO)₂(CH₃CN), AsPh₄[ReCl₄(NO)₂] ReCl₃(NO)₂, which is associated via chlorine bridges, was obtained in quantitative yield from rhenium pentachloride and trichloro nitromethane. Using acetonitrile, the monomer complex ReCl₃(NO)₂(CH₃CN) can be obtained from it, from which AsPh₄[ReCl₄(NO)₂] arises with tetraphenylarsoniumchloride. The i.r. spectra are reported and assigned. The crystal structures were determined for the latter two compounds with the help of X-ray diffraction data. ReCl₃(NO)₂(CH₃CN) crystallizes in the monoclinic space group P2₁/n with four molecules per unit cell, AsPh₄[ReCl₄(NO)₂] crystallizes in the tetragonal space group P4/n with two formula units. In all three compounds, the two NO groups linked to a Re atom are arranged cis to one another. As the anion in AsPh₄[ReCl₄(NO)₂] is situated on a fourfold axis, the cis-configuration causes a statistical disorder in the crystal.     

Mass spectrometric investigation of stereosomeric 1,2-dimethyl-4-substituted decahydroquinol-4-ol N-oxides. Concerning the configuration of the asymmetric nitrogen atom

The main fragmentation pathways of the N-1, C-2 and C-4 stereoisomers of the 1,2-dimethyl-4-R-transdecahydroquinoline-4-ol N-oxides (R=C?CH, CH?CH₂ and C₂H₅) under electron impact are discussed. The correlation between the mass spectrometric chromatographic behaviour and the configuration of polar groups in the N-oxides examined is discussed. The mass spectra of the N-1 stereoisomers may be subdivided into two groups, depending only on the orientation of N→O group and not of the 4-OH group. The spectra of N-oxides with the axial N-oxide group reveal less intense ions and much more intense [M? CH₃]⁺, [M? O]⁺, [M? OH]⁺ and ions, whereas in the spectra of their equatorial epimers the abundance of the ions exceeds the intensities of the latter ions.     

o.Formylarylazomethylenetriphenylphosphoranes: A facile thermally promoted rearrangement to 3-oxo-indazoline and 4-oxo-dihydroquinazoline derivatives

The $\text{o}$.formylarylazomethylenetriphenylphosphoranes carrying an electron withdrawing group on the ylidic carbon undergo thermal $\text{intra}$ molecular cyclization to 3-oxo-indazolin-2-yl-methylenetriphenylphosphorane derivatives. The latter compounds, and their 1-alkyl derivatives, in turn, undergo thermal and/or acid catalyzed rearrangement to 4-oxo-l,4-dihydroquinazoline derivatives and PPh₃. Some possible reaction mechanisms are discussed, and some synthetic applications of the above reactions are shown.     

Cs[Ag4Zn2(SCN)9]

Caesium tetrasilver dizinc nona­thio­cyanate, Cs[Ag₄Zn₂(SCN)₉], forms a continuous structure, where the Ag atoms and the S atoms of the thio­cyanate groups form chains which run along [101]. These chains are bonded together through the Cs and Zn atoms. It is not possible to distinguish between space groups P1 and P, but, if the latter space group is correct, the structure contains a thio­cyanate group disordered across a centre of inversion. The structure is described in space group P, in which the Cs atom also lies on a centre of inversion.     

Syntheses,Crystal Structures,and Properties of the Novel Thioborates KBa4(BS3)3 and K4Ba11(BS3)8S

Our systematic studies on quaternary thioborates containing both a comparably small alkali metal ion and a large alkaline earth cation lead to the two new crystalline phases KBa₄(BS₃)₃ and K₄Ba₁₁(BS₃)₈S. The former consists of isolated BS₃ units and the corresponding counter‐ions while in the latter BS₃^3– and S^2– anions coexist. In both compounds boron is found in a trigonal‐planar coordination, in the case of K₄Ba₁₁(BS₃)₈S the additional sulfide anions are located inside an octahedron built of six barium cations. The two compounds were prepared in solid state reactions from the metal sulfides, amorphous boron and sulfur. Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. KBa₄(BS₃)₃ crystallizes in the monoclinic space group C 2/c (no. 15) with a = 14.299(6) Å, b = 8.808(3) Å, c = 13.656(5) Å, β = 98.72(4)°, and Z = 4, while for K₄Ba₁₁(BS₃)₈S the trigonal space group R 3 c (no. 167) was found with a = 18.146(3) Å, c = 25.980(7) Å, and Z = 6. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination, in the case of K₄Ba₁₁(BS₃)₈S vibrational spectra were recorded.     

Isomerization of 4-amino-2-sulfolenes

The base-catalyzed isomerization of 4-arylamino- and 4-morpholino-2-sulfolenes to 3-substituted 2-sulfolenes was investigated by UV spectroscopy. A shift in the _as frequencies of the SO₂ group was noted in the IR spectra of the latter.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 627–630, May, 1975.     

An SCF study of P4O6 and P4O10

The electronic structures of the oxides P₄O₆ and P₄O₁₀ are calculated by the self-consistent molecular orbital method including all valence electrons and the 3d orbitals on phosphorus. It is found that the former molecule appears to be virtually non-polar whilst in the latter, the P-O (terminal) bonds are highly polar. The bond order matrix shows that the internal P-P bonding in the P₄ unit is not marked.     

Preparation,crystal structure,and infrared characterization of the first thiocyanato-oxy-antimonate(III) [(CH3)4N]2[Sb6O4(NCS)12]

The salt [(CH₃)₄N]₂[Sb₆O₄(NCS)₁₂] is the first identified thiocyanato-oxy-antimonate(III) complex. Reported are details of the synthesis, relevant infrared data and its x-ray structure. The compound crystallizes in the triclinic space group P1 with Z = 2 (C₁₀H₁₂N₇O₂S₆Sb₃) and unit cell dimensions a = 11.314(6), b = 12.846(3), c = 8.679(2) Å; α = 91.93(3)°, β = 90.31(3)° and γ = 99.13(3)°. It contains centrosymmetric [Sb₆O₄(NCS)₁₂]^2? anions packed with isolated tetramethyl-ammonium cations. The fundamental structural element of the anion is provided by the fusion of three SbOSbO rings forming a zig-zag portion of a ribbon, only slightly pleated. Peculiar is the unequivalence of the six thiocyanate ligands, though all primarily N-bonded to antimony atoms. Three thiocyanates are terminal while other three are asymmetrically N-bridging between two centers; two of this latter type are also interconnecting the anions via Sb???S contacts. There are three different antimony environments, the primary bonding at Sb being to one nitrogen and three oxygens, to one oxygen and three nitrogens and to two atoms of each type.     

Oxidation and nitrosation of 4-(3-alkylureido)-2, 2, 6, 6-tetramethylpiperidine-1-oxyls to 4-(3-alkyl-3-nitrosoureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium salts

4-(3-Alkylureido)-2, 2, 6, 6-tetramethylpiperidine-1-oxyls are rapidly oxidized by N₂O₄ or NOCl to 4-(3-alkylureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium nitrates and chlorides, which are then nitrosated to 4-(3-alkyl-3-nitrosoureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium salts. The perchlorates of the latter were prepared by an exchange reaction with HClO₄. The nitrosation of alkylureidooxoammonium salts is the first example of chemical modification of oxoammonium derivatives in which the highly reactive >N⁺=O group is inert toward the reagent.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 542–547, March, 1993.     

Ruthenium complexes of 3-hydroxy-4-pyranones and of 3-hydroxy-4-pyridinones

Reactions of hydrated ruthenium chloride with 2-methyl-3-hydroxy-4-pyranone, ethylmaltol (etmaltH) and with 1,2-dimethyl-3-hydroxy-4-pyridinone (dmppH) are described. The former results in the formation of Ru(etmalt)₃, but the course of the latter depends on conditions, producing the earlier-characterised Ru(dmmp)₃Cl in ethanol–water solution, Ru(dmmp)₃ in aqueous solution under mild conditions, and Ru(dmpp)₂(H₂O)₂ after extended refluxing. EXAFS studies established ruthenium-oxygen distances in Ru(etmalt)₃ and in Ru(dmmp)₃ · 6H₂O. Solubilities of Ru(dmmp)₃ in methanol–water mixtures reveal greater solubility in methanol than in water, and indications of a modest solubility maximum, and thus synergic solvation, in methanol-rich mixtures.     

Some new observations on the luminescence of PbMoO4 and PbWO4

We report on the luminescence of doped and undoped PbMoO₄ and PbWO₄ single crystals; a red emission is found for the first time for PbMoO₄. The degree of polarization of both the emissions of PbWO₄ and of the shorter-wavelength emission of PbMoO₄ is measured. The shorter-wavelength emissions are assigned to the ³T₁¹A₁ transition in the tetrahedral MoO₄^2?(WO₄^2?) group. It is assumed that the ³T₁ level is split due to spin-orbit coupling. The longer-wavelength emissions are assigned to a transition in a molybdate (tungstate) group lacking an oxygen ion, i.e., a MoO₃(WO₃) group.     

Die Kristallstruktur von LiEu3O4

The crystal structure of LiEu₃O₄ which represents a new structure type was solved by usual methods with the aid of integrated WEISSENBERG photographs (MoK_α radiation, 787 reflexions) and refined to a reliability index of 4.3%. In LiEu₃O₄ just as in the first known europium(II, III)-oxide, Eu₃O₄, a clear distinction is possible between the divalent and trivalent europium ions. The given assignment which is based on crystal chemical arguments has been verified indirectly by means of the isostructural compound LiSr₂EuO₄, the cation distribution of which was established experimentally. The structure of LiEu₃O₄ is discussed in connection with the related oxides EuO and Eu₃O₄. The geometrical relations to the latter are of special interest, as LiEu₃O₄ undergoes a topotactical transformation into Eu₃O₄ by heating it in a high vacuum. There is an astonishing close structural relationship between LiEu₃O₄ and Yb₃S₄: except for lithium all the atoms are correlated as for isostructural compounds.     

19F NMR study ofcis- andtrans- effects of substituted triphenylphosphine ligands intrans-(4-fluorophenyl)triarylphosphine-tri(4-fluorophenyl)phosphineplatinum 4-fluorothiophenoxides

A number of compounds of the type oftrans-4-FC₆H₄Pt(PAr₃)₂SC₆H₄F-4, where Ar is a substituted phenyl group, have been prepared starting from the corresponding chlorides. By exchange reactions oftrans-4-FC₆H₄Pt[P(C₆H₄F-4)₃]₂SC₆H₄F-4 with the above-mentioned compounds or Ar₃P,trans-4-FC₆H₄Pt[P(C₆H₄F-4)₃][PAr₃]SC₆H₄F-4 have been generated in solution. For the latter compounds, the effect of Ar₃P oncis- andtrans-ligands has been studied by the¹⁹F NMR technique. It has been shown that thecis- andtrans-effects of Ar₃P run parallel and are well described by pK _a values and ionization potentials of the unshared electron pair in Ar₃P, as well as by ⁰ constants of the aryl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1359–1363, July. 1995.     

Synthese von 2-Hydeoxy-3-methyl-2-hexen-4-olid

Synthesis of 2-Hydroxy-3-methyl-2-hexen-4-olid The title compound 13a, a substance used in food-flavoring, was synthesized in 89% overall yield, starting from methyl 2-hydeoxy-3-butenoate (3_a). The key step in this transformation is the isomerization of the C?C bond in 3_a which yielded methyl 2-oxobutanoate as an intermediate. The latter underwent a self-condensation yielding 2-hydroxy-4-(methoxycarbonyl)-3-methyl-2-hexen-4-olid ( 11 _a), which, after hydrolysis and decarboxylation, gave 13 _a. In addition, the syntheses of five other compounds related to 13 _a are reported.     

[{Cp(CO)3Mo}4In4(PSiMe3)4], Ein metallorganisch substituiertes In4P4-Heterokuban

[{Cp(CO)₃Mo}₄In₄(PSiMe₃)₄], an Organometallic In₄P₄-Heterocubane [{Cp(CO)₃Mo}InCl₂] reacts with P(SiMe₃)₃ in THF as solvent to form [{Cp(CO)₃Mo}₄In₄(PSiMe₃)₄] 1. 1 crystallizes in the space group P1 . The lattice constants (at 208 K) are: a = 1 770.1(6), b = 1 490.3(6), c = 1 317.5(6) pm, α = 76.59(4),β = 88.54(3), γ = 88.98(3)°. According to the crystal structure analysis, 1 contains a slightly distorted In₄P₄-core with an alternating arrangement of In and P atoms. The In atoms are coordinated roughly tetrahedrally by three PSiMe₃ groups (In–P: 256.9(3)–262.3(3) pm) and a {Cp(CO)₃Mo} substituent (In? Mo: 278.0(2)–279.5(3) pm).     

Preparation et etude d'un oxyphosphate Fe4(PO4)2O

This compound is obtained in several ways, at 900°C, from the components of the FePO system when the oxygen pressure is made suitable, or from Fe₃(PO₄)₂ + Fe + Fe₂O₃ in a sealed tube under vacuum. It crystallizes under these latter conditions with a trace of FeCl₂. The cell is monoclinic; a = 6.564(1), b = 11.271(2), c = 9.383(2) Å, β = 103.95 (2)°, with Z = 4, group $\text{P2}{}_1\text{c}$. The structure is determined thanks to the use of a direct method and Fourier synthesis and is refined to R = 0.033. The PO₄ tetrahedra are isolated; the iron fills four crystallographic sites: three are more or less distorted octahedra, the fourth is a trigonal bipyramid. The oxyphosphate character is ascertained by the presence of some oxygen atoms connected to iron only, with, moreover, a low site potential. This compound is paramagnetic above 90°K. Its Mössbauer spectrum exhibits four doublets in good agreement with the structure; in order to identify which one corresponds to the hexahedral site, the phase Fe₃Zn(PO₄)₂O has been prepared, but its Mössbauer spectrum, in spite of the zinc affinity for the V coordination, shows that two sites are modified, which does not allow conclusions to be made.