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1.
Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1–40%) in the absence of glass readily gives triphenylarsine difluoride. When the reaction with dilute (1%) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO·HBF4. Crystals of this compound are monoclinic, P21/c, a = 12.926(4), b = 17.819(6), c = 14.994(4) Å, β = 98.97(3)°, Z = 4. The structure contains cations [(Ph3AsO)2H]+ in which O?O is 2.44(2)Å, and anions BF4?.  相似文献   

2.
1,2,3,4,7,7-Hexafluorobicyclo[2,2,1]hepta-2,5-diene gave 1,2,3,4-tetrafluorebenzene in at least 73% yield when heated to 450°C in a sealed tube; the CF2 bridge appeared, in part, as octafluorocyclobutane. Nucleophilic attack by sodium methoxide- methanol on the diene occurred exclusively at the CFCF bond, causing the formation of 1,2,4,7,7-pentafluoro-3-methoxybicyclo- [2,2,1]hepta-2,5-diene and a 1,4,5,6,7,7-hexafluoro-5-methoxybicyclo [2,2,1]hept-2-ene thought, on the basis of 19F nmr data, to be the 6-endo-F,5-exo-MeO isomer. Radical attack on 1,2,3,- 4,7,7-hexafluorobicyclo[2,2,1]hepta-2,5-diene by bistrifluoromethyl nitroxide took place at both olefinic sites, with a ca. 10:1 preference for the CFCF linkage; all three geometrical isomers of 5,6-bis(bistrifluoromethylamino-oxy)-1,4,5,6,7,7- hexafluorobicyclo[2,2,1]hept-2-ene were formed.  相似文献   

3.
Crystal structures of the ordered phases of V3S4 and V5S8 were refined with single crystal data. Both are monoclinic. Chemical compositions, space groups and lattice constants are as follows: VS1.47, I2m (No. 12), a = 5.831(1), b = 3.267(1), c = 11.317(2)Å, β = 91.78(1)° and VS1.64, F2m (No. 12), a = 11.396(11), b = 6.645(7), c = 11.293(4), Å, β = 91.45(6)°. In both structures, short metal-metal bonds were found between the layers as well as within them. In comparison with the structure of Fe7S8, the stability of NiAs-type structure was discussed based on the detailed metal-sulfur distances.  相似文献   

4.
Direct chlorination of 2-(2H-hexafluoropropyl)-tetra- hydrofuran 1 gave high yield of 2-(2-chlorohexafluoropropyl)- pentachloro-2,5-dihydrofuran 2. Bromination of 1 gave very complex mixture of products, from which three compounds, viz. 2-bromo-5-(2H-hexafluoropropyl)-furan 3, 3-bromo-5-(2H-hexafluoropropyl)-furan 4, and 2,4-dibromo-5-(2H-hexafluoropropyl)furan 5 were isolated. Exchange fluorination of 2 with dry KF at 240 – 300° led to a stepwise substitution of fluorines for chlorines to give mixtures of chloro-fluoro-2-(2-chlorohexafluoropropyl)-dihydrofurans 7,8,9 and 10, together with small amounts of 2-(2-chlorohexafluoropropyl)-3,4,5-trichlorofuran 6.Exchange fluorination of 3,4-dihalo-2,2,5,5-tetrafluoro- 2,5-dihydrofurans 11a and 11b led to a substitution of fluorine for one vinylic halogen to give 3-halo-2,2,4,5,5-pentafluoro-2,5-dihydrofurans 12a and 12b in good yields.Compounds 212 were characterised by n.m.r., m.s., and i.r. spectroscopy and elemental analysis.  相似文献   

5.
The reaction of titanocene dichloride with disodium fumarate in the two-phase system H2O/CHCl3 yields bis(μ-fumarato)bis[di(π-cyclopentadienyl)titamum(IV)]. Crystal data for the pure compound (IIIa): monoclinic, P21/n, a 18.558(5), b 9.076(5), c 7.559(2) Å, β 101.69(2)°; Z = 2. Crystal data for a phase containing chloroform of crystallization (CHCl3/Ti = 11) (IIIb): triclinic, P1, a 20.439(11), b 10.269(5), c 8.858(3) Å, α 112.18(3), β 93.93(5), γ 91.63(7)°; Z = 2 × 1. The three independent [(π-C5H5)2TiOCOCHHOCO]2 molecules differ in the puckering of their 14-membered rings and the geometry of their TiOC units.  相似文献   

6.
In CFCl3, aziridines I react with F2(6 %/N2,  20°C), COF2 (20 %/N2,  40°C) and CF3OF [1] (20 %/N2,  40°C).Substitution products are obtained : l-(aziridine)carbonyl fluorides II and l-Fluoroaziridines III
In (Et)2O, aziridines I react with COF2 (20 %/N2, 10°C) and we have the carbonyl fluorides IV.
Products IV can be thermally decomposed into β fluoro isocyanates.In CFCl3, N substituted aziridines V react with F2(6%/N2, 20°C) and with CF3OF [2] (20%/N2, 40°C). No reaction is observed with COF2in our conditions (5% to 25%/N2, 80°C to + 40°C).Addition products are obtained : N Fluoro amines β fluorinated VI, N Fluoro and NN difluoro amines β trifluoro methoxylated VII and VIII.
with R = SO2Ø, COØNO2, Cl.  相似文献   

7.
The structure of [Pt2Cl(CO) (μ-Ph2PCH2PPh2)2] [PF6] was determined by X-ray methods and refined to R = 0.082, using diffractometric intensities of 5646 independent reflections. The crystals are monoclinic, space group P21/n, a = 12.919(3), b = 15.576(6), c = 25.151(5)Å, β = 94.82(3)°, Z = 4. They are built of octahedral hexafluorophosphate anions and dinuclear platinum(I) cations. The latter contain PtCl and PtCO fragments linked to one another by a PtPt σ-bond and by two bridging bis(diphenylphosphino)methane ligands. The platinum atoms are in square planar environments and the dihedral angle between the two coordination planes is 40.1°. Selected bond lengths are: PtPt 2.620(1), PtCl 2.384(5), PtC 1.89(3) and PtP 2.291(5) – 2.308(5)Å.  相似文献   

8.
The two perfluoro-azadienes CF2N.CRCF2 (R = CF3 or CF2Cl) show temperature dependent 19F n.m.r. spectra, with non-equivalent fluorine nuclei of the CF2N portion at low temperatures, which coalesce due to inversion at the nitrogen at higher temperatures (ΔG3 = 60 kJ mol?1). N.m.r. parameters have been obtained. One of the five-bond FF coupling constants is much larger (ca. 24 Hz) than the remainder (0·5–5·5 Hz), possibly due to ‘through-space’ coupling of fluorines in the cis-skew conformation.  相似文献   

9.
The vapour phase reaction of ammonia and hexafluoroacetylacetone leads to the formation of the new β-keto-amine C5H3F6NO. Crystals of the compound are monoclinic, space group P21/n, a = 10.01(2), b = 19.33(3), c = 8.40(1) Å, β = 82.27(6)°; final R = 0.044.  相似文献   

10.
11.
The structures of 5-methyl-5-phenyl-5H-dibenzo[b,f] silepin (I) and 5-methyl- 5-phenyl-1O,11-dihydro-5H-dibenzo [b,f] silepin (II) have been determined from three-dimensional X-ray data collected by counter methods. I crystallizes in the orthorhombic space group Pnam with a 7.596(3), b 18.102(5) and c 12.190(2) Å; observed and calculated densities (Z = 4) are 1.17 and 1.18 g cm?3, respectively. II crystallizes in the monoclinic space group P21c with a 11.115(3), b 7.920(3), c 20.765(5) Å and β 111.71(2)°; observed and calculated densities (Z = 4) are 1.17 g cm?3. Anisotropic refinement of nonhydrogen atoms, with hydrogen atoms included at fixed ideal locations, gave conventional R-factors of 4.5% (I) and 5.0% (II). Compound I exhibits the boat conformation for the tricyclic framework and is located on a crystallographically required mirror plane. Com- pound II has the expected folded boat conformation. The torsion angle about the 10,11-bond is 0.0° for I, a crystallographic symmetry requirement, and 89.9° for II. Mean SiC bond distances are 1.863 Å(I) and 1.875 Å(II). The dihedral angles between the planar benzo groups are 129.7° (I) and 137.2° (II); introduc- tion of unsaturation at the 10,11-position decreases the dihedral angle in the tri- cyclic system, i.e., the tricyclic system is more bent.  相似文献   

12.
The crystal structure of Na[N{Si(CH3)3}2] has been determined from single-crystal x-ray diffraction data collected by counter methods. N-sodiohexamethyldisilazane crystallizes in the mono-clinic space group p21/n with unit cell parameters a = 9.426(3), b = 6.921(3), c = 17.974(5)Å, β = 93.83(2)°, and ?calc = 1.04 g cm?3 for z = 4 formula units. Least-squares refinement gave a final conventional R value of 0.034 for 1244 independent observed reflections. In the solid state the compound exists in a polymeric arrangement with an average Na-N distance of 2.355(4)Å. The methyl group are configured such that the angle of rotation of the trimethylsilyl moiety about the Si-N bond is 30° from the eclipsed position. The Si-N bond length is 1.690(5)Å, and the Si-N-Si bond angle is 125.6(1)°.  相似文献   

13.
The title compound is the final product of the reaction between dimethylacetylene dicarboxylate and [(η5-C5H5)W(SMe) (CO)3 ]. Its molecular structure has been established by an x-ray analysis based on 3301 diffractometric intensities. The crystals are monoclinic, space group P21/a, with four molecules in a cell of dimensions a = 10.323(2), b = 16.016(2), c = 10.437(2)», β = 103.56(2)°. After least-squares refinement R = 0.036. The tungsten co-ordination is square-pyramidal, the apical site being occupied by the centroid of the cyclopentadienyl ring. The basal co-ordination sites contain two carbonyl groups and also the sulphur and σ-bonded carbon atoms of a chelating carbothiolic methyl ester ligand derived from the incoming alkyne and CO and SMe groups of the original complex. The W-S and σ-W-C bond lengths are 2.440(2) and 2.194(7)».  相似文献   

14.
Form I of poly(hexamethylene terephthalate), poly(6GT), has been shown, through electron diffraction of micro-single crystals, and fibre X-ray diffraction to belong to the triclinic system. The unit cell containing only one chain has dimensions a = 5.217(8), b = 5.284(12), c = 15.738(16) A? (fibre axis), α = 129.4(2), β = 97.6(2) and γ = 95.6(2)°. The space group is PT. The crystal structure of poly(6GT) form I has been established by the model compound approach and confirmed using 19 independent electron diffraction intensities. Upon refinement of the scale and temperature factors, the agreement index R reaches 0.172, with an overall isotropic temperature factor B = 3.0 A?2. Calculation of dynamical amplitudes, and also of structure amplitudes which allow for crystal bending, confirms that the electron diffraction data are suitable for a conventional structure analysis. The chain of the polyester has the same fully extended conformation as its related model compound hexamethylene glycol dibenzoate. The planar chain in the single cell is at 35° to the α-axis. The unit-cell dimensions of poly(6GT) form II differ from those of form I by the doubling of the b-dimension. The two chains in the double unit-cell are at 31 and 39° respectively from the a-axis. The agreement index R is 0.161 for the 19 reflections of the single cell and R = 0.196 when the 10 reflections causing the doubling of b are included.  相似文献   

15.
Vacuum Flash Pyrolysis (VFP) at ca. 450–500°C and ca. 0.1–0.3 Torr of the spirocyclic malonyl peroxides (2a,b) affords high yields of allenes (5a,b), while the simple malonyl peroxide (2c) leads to ketone (4), derived respectively from decarboxylation and decarbonylation of the intermediary α-lactones (3).  相似文献   

16.
The title compound is isolated from reaction of hexafluorobut-2-yne with μ-μ-Dichlorobis(cycloocta-1,5-diene)diiridium(I) at 90°C. Crystals of the complex, solvated with deuterobenzene, are monoclinic, space group P21/n with a = 10.97 + 0.02, b = 17.96 + 0.03, c = 11.63 + 0.02 », β = 127.4 + 0.60°. The acetylene has abstracted a hydrogen atom forming a σ-bonded cis-vinylic group and the original cyclooctadiene, having lost a proton, is coordinated as the cycloocta-1,5-dienyl ligand. Mean bond lengths are IrCl 2.467, IrC (allylic) 2.17, IC (olefinic) 2.36 and IrC (vinylic) 2.09 ».  相似文献   

17.
Phosphorus pentafluoride was reported long ago to give adducts 2 PF5 ·5 NH3 (1) and nNH3·PF5 (n= 1 ? 4) (2). None of the compounds was characterised in detail. Repeating the reaction of PF5 and NH3 we found the adduct H3N·PF5, 1, in 8% yield besides (H2N) 2PF3 (3) and NH4PF6. However, HF and (F2P=N)3 gave 1 in 41% yield. The 1H, 19F, and 31P n.m.r. spectra of 1 exhibit 14NH, 14NPF(cis), and 14NP coupling. The x-ray structure determination shows almost perfect octahedral geometry at phosphorus with a PN bond length of 1.842 ā. Compound 1 is soluble in water without decomposition. Treatment with NH3 leads to the anion H2NPF5?. Upon heating 1 forms in good yield H2NPF4 and NH4PF6. Without a solvent 1 and NH3 react to give (H2N) 2PF3. A mechanism for the ammonolysis of PF5 is proposed.  相似文献   

18.
In the reaction of Cp2WGl2 with Li[Si(SiMe3)3] the dihydrid tungstenocene derivative [(Me3Si)3SiC5H4]WH2 (3) is formed with a 56% yield. 3 crystallizes in space group P1, with a 918.0(4), b 1580.9(4), c 1621.2(7) pm, α 117.63(2), β 89.95(3), γ 94.39(3)° at ?40° C. The dihedral angle between the Cp planes is 140.9°.  相似文献   

19.
The crystal structure of a bis(triphenylphosphine)iminium salt of the 1:1 adduct of [FeH(CO)4]? and dimethyl acetylenecarboxylate has been determined from three-dimensional X-ray data collected by the counter method. Single crystals belong to the triclinic space space group P1, with two units of [C36H30NP2]+[C10H7FeO8]? in a cell of dimensions: a = 13.918(2), b = 15.669(5), c = 9.909(2) Å, α = 91.22(3), β = 94.83(2), and γ = 77.62(2)°. The structure was refined to a conventional R of 0.068 for 5373 observed
reflections. The resulting structure indicates that the complex anion is η3-[trans-2,3-bis(methoxycarbonyl)acryloyl]tricarbonylferrate, the coordination around the iron atom being described as a considerably distorted trigonal bipyramid. A comparison of the present structure with the structures of related complexes suggests that the η3-acryloyl portion is best represented as an intermediate of (η3-allyl) with the oxygen atom and (η2-olefin + η1-acyl). The short Fe-C(acyl) length of 1.897(5) Å implies an enhanced back-donation of electrons from the iron atom to the acyl group.  相似文献   

20.
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