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1.
The α-distonic sulphur-containing ion $ {}^ \cdot {\rm CH}_2 \mathop {\rm S}\limits^ + \left({{\rm CH}_3 } \right)_2 $ has been generated by transfer of CH from ionized oxirane to dimethyl thioether and distinguished from the molecular ion of ethyl methyl thioether by collision induced dissociation (CID) experiments. In particular, the α-distonic ion expels CH2 to a minor extent following collision, whereas the molecular ion of ethyl methyl thioether does not undergo this reaction. The metastable C3H8S ions formed by CH transfer to dimethyl thioether and ionization of ethyl methyl thioether decompose by competing losses of CH3R˙, CH4 and C2H4. The elimination of ethene is taken as evidence for isomerization of the α-distonic ion to the molecular ion of ethyl methyl thioether prior to spontaneous dissociation. Evidence for the formation of stable α-distonic sulphur-containing ions by transfer of CH from ionized oxirane to methyl phenyl thioether has not been obtained. The collision-induced and spontaneous reactions of the ions formed by CH transfer to methyl phenyl thioether indicate that a mixture of the radical cations of CH3C6H4SCH3, C6H5SCH2CH3 and C6H5CH2SCH3 is generated implying that attack on the phenyl group occurs in addition to a formal insertion of a methylene entity in a C? S bond.  相似文献   

2.
The haloacetyl ions [XCH2CO+], X = Cl, Br, I, have been produced by the dissociative ionization of selected precursor molecules and identified via their fragmentation characteristics. Their heats of formation, Δ, were 708 ± 8, 750 ± 25 and 784 ± 10 kJ mol?1, respectively, all appreciably above ΔH for [CH3CO+], 653 kJ mol?1. The effect of halogen substitution α to carbonyl is discussed for neutral molecules and their molecular ions.  相似文献   

3.
The Unimolecular mass spectrometric fragmentations of the molecular ions of 1,3-diphenylpropane, 1-(7-cycloheptatrienyl)-2-phenylethane and the 1-phenyl-2-tolylethanes and their [d5]phenyl analogues have been investigated by metastable ion techniques and measurements of ionization and appearance energies. By comparing the formation of [C7H7]+, [C7H8]+?, [C8H8]+? and [C8H9]+ it is shown that the molecular ions of the four diaryl isomers do not undergo ring expansion reactions of the aromatic nuclei prior to these fragmentations. Conversely, the molecular ions of the cycloheptatrienyl isomer suffer in part a contraction of the 7-membered ring. From these results and from the measured ionization and appearance energies lower limits to the activation energies of these skeletal isomerizations have been estimated yielding E > 33±5 kcal mol?1 formonoalkylbenzene, E > 20 2±5 kc mol?1 for 7-alkylcycloheptatriene and E > 40±5 kcal mol?1 for dialkylvbenzene positive radical ions. Upper limits can be deduced from literature evidence yielding E < 45 kcal mol?1 for monoalkylbenzene and E < 53 kcal 4mol?1 for dialkylbenzene positive radical ions. The activation energy thus estimated for monoalkylbenzene is in excellent agreement with the recently calculated value(s) for the toluene ion.  相似文献   

4.
Vibration spectra and force constants of the series O2PF — S2PF — S2P(CH3). The vibrational spectra of OSPF, S2PF, S2PF(CH3) and S2P(CN) are reported and discussed with O2PF and S2P(CH3). On the basis of a simplified valence-force-field the force constants are calculated and the bonding relations are discussed. In the ions, f PF is lower than in corresponding molecules. The ionic charge is distributed over nearly all atoms of the ions.  相似文献   

5.
Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu4N)2[(W6Cl )F ] · 2 CH2Cl2 and 19F NMR Spectroscopic Evidence of the Mixed Cluster Anions [(W6Cl )F Cl ]2–, n = 1–6 The reaction of (n‐Bu4N)2[(W6Cl)Cl] with CF3COOH in dichloromethane gives intermediately a mixture of the cluster anions [(W6Cl)(CF3COO)Cl]2–, n = 1–6. By treatment with NH4F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series [(W6Cl)FCl], n = 1–6 are formed and characterized by their distinct 19F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(WW) = 1.89, fd(WF) = 2.43 and fd(WCl) = 0.93 mdyn/Å.  相似文献   

6.
Ultraviolet absorption spectra have been characterized for the acetyl-h3 and acetyl-d3 radicals, which were generated by the flash photolysis of the corresponding acetones. The spectra are broad and intense, with values of the extinction coefficient at the respective maxima estimated as: ?CH3CO(215) = (1.0 ± 0.1) × 104 L/mol·cm and ?CD3CO(207.5) = (1.0 ± 0.05) × 104 L/mol·cm. Rate constants for the reactions of mutual interaction were estimated as: k = 3.5 × 1010 L/mol·s and k = 3.4 × 1010 L/mol·s. Rate constants for the reactions of cross interaction were estimated as: k = 8.6 × 1010 L/mol·s and k = 5.2 × 1010 L/mol·s. The related values of the cross interaction ratios k/(kk)1/2 = 2.6 and k/(kk)1/2 = 1.6 do not differ significantly from the statistical value of 2. The participation of the radical displacement reactions was estimated in terms of the fractions k/k = 0.38 and k/k = 0.47. Corroborative spectra were obtained from the flash photolysis of methyl ethyl ketone and biacetyl, and the relative rates of the competing primary processes were estimated from the relative peak heights of the acetyl and methyl radicals in each system.  相似文献   

7.
Isomerization of oxime molecular ions into nitrone molecular ions upon electron impact does not generally occur, but it was established with the aid of deuterium labelling that it is essential for loss of CH from o-methylbenzaldoxime.  相似文献   

8.
Cationic polymerization of tetrahydrofuran (THF) in CH2Cl2 solvent and in mixed CH2Cl2/CH3NO2 solvent was initiated with 1,3-dioxolan-2-ylium cations with AsF and SbF anions. Dissociation constants of the polytetrahydrofuranium ion pairs into ions were measured (e.g., KD = 1.5 × 10?5M at 25°C and [THF]0 = 7.0M; CH2Cl2 solvent) and were found to be more than 100 times lower than in CH3NO2 solvent at the same [THF]0 and temperature. The rate constants k and k, measured for degrees of dissociation ranging from 0.03 to 0.35 in CH2Cl2, were the same within an experimental error of measurements (±15% of the value of kp). Dependence of k( = k = k) on the dielectric constant was a monotonous function in three different solvents, namely, CCl4, CH2Cl2, and CH3NO2, which covered a large range of dielectric constants of the medium (from D = 5 to D = 22) and degrees of dissociation of the macroion pairs, α (from 0.03 to more than 0.70). Thus a decrease in the dielectric constant increases the rate constant k in the whole range of studied polarities of the medium. This result confirms an earlier conclusion that the rate constant of propagation does not depend on the state of aggregation of ions and k = k.  相似文献   

9.
The rate of the reaction CH2I2 + HI ? CH3I + I2 has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k1/M?1 sec?1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E2 = 0 ± 1 kcal/mole, leads to ΔH (CH2I, g) = 55.0 ± 1.6 kcal/mole and DH (H? CH2I) = 103.8 ± 1.6 kcal/mole. The kinetics of the disproportionation, 2 CH3I ? CH4 + CH2I2 were studied at 331° and are compatible with the above values.  相似文献   

10.
Doubly charged molecular anions M2? of fullerenes are formed in the gas phase under chemical ionization conditions with isobutane as the reagent gas. The efficiency of double electron attachment increases with increasing size of the fullerenes: the C ion is the most abundant doubly charged anion in the negative-ion CI mass spectrum, although the concentration of C70 was about 12% in the fullerene mixture examined. Under low-energy collision-induced dissociation conditions an electron is ejected from the doubly charged C ion resulting in the singly charged molecular anion C˙. This process appears to be the first report of the ejection of an electron (electron stripping) from a doubly charged anion in the gas phase: .  相似文献   

11.
19F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo6Br Cl )F ]2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo6BrCl)4+ is formed by exchange of innersphere bound Cli against outersphere bound Bra on tempering the solid [(Mo6Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H3O)2[(Mo6BrCl)Cl] and precipitation of the outer Cla with AgBF4 in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)2 [(Mo6BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 19F nmr signals are expected, which are really observed in the high resolution 1D-19F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-19F/19F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers.  相似文献   

12.
The reactions indicated in the title have been studied in terms of direct processes and complex formation. Quantum-chemical methods have been applied to the passage of an acid (H+, CH, X+) from CH3X to CH3X, and the abstraction of a radical (H· CH, X·) from CH3X by CH3X. It has been shown that a complex represented by a dimer of a methyl-halide radical cation, (CH3X), with a two-center three-electron bond X? X, has fairly high stability. These investigations were based on non-empirical quantum-chemical calculations, the results being systematically compared with experimental determinations. Some calculations included all electrons (X=F, Cl, Br), others were based on relativistic pseudopotentials (X=F through At). The two sets of calculations agree qualitatively with each other and with experimental observations.  相似文献   

13.
Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph3P)2N]2[(W6Cl )I ] · 2 Et2O · 2 CH2Cl2 and [(Ph3P)2N]2[(W6Cl )(NCS) ] · 2 CH2Cl2 By treatment of [(W6Cl)I]2– with (SCN)2 in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W6Cl)(NCS)]2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph3P)2N]2[(W6Cl)I] · 2 CH2Cl2 · 2 Et2O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2 ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (νCN), 879–867 (νCS) and 490–482 (δNCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu4N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are fd(WW) = 1.61, fd(WI) = 1.23 and fd(WCl) = 1.10 mdyn/Å.  相似文献   

14.
Silaheterocycles. III. Synthesis and Reactivity of Di-tbutylneopentylsilaethene, Bu Si?CHCH2But The three di-tbutylvinylsilanes BuSi(X)CH?CH2 (X = H 5 , X = F 9 , X = Cl 22 ) are prepared by the reaction of their SiCl precursors with vinyl lithium. In the treatment with LiBut the first step is the generation of the α-lithio compound BuSi(X)CH(Li)CH2But, the following reactions are governed by the nature of the substituent X and the reaction conditions (solvent, concentration, temperature). For X = H 2,3-LiH elimination leads to BuSi(H)CH?CHBut ( 7 ), with X = F or Cl Si?C formation by 1,2-LiX elimination competes with intermolecular Si-C-coupling producing BuSi(H)CH(SiBuCH?CHBut)CH2But ( 13 ) as the main product. BuSi?CHCH2But ( 1 ) probably coordinates to LiBut and reacts to yield BuSiCH?CHBut ( 3 ) and 7 , forms tetrabutyl-dineopentyl-1,3-disilacyclobutane 2 by cyclodimerization and 13 by addition of BuSi(X)CH(Li)CH2But.  相似文献   

15.
On Ordered Perovskites with Cationic Vacancies. XI. Compounds of Type A B B □1/4WVIO6 ? A BIIB □W O24 with AII, BII = Ba, Sr Depending on the ionic radii of the two and three valent cations in the perovskites of type ABB □1/4WVIO6 ?; ABIIB □WO24 order disorder phenomena are present. The results of the x-ray and vibrational spectroscopic investigations as well as the diffuse reflectance spectra and the visible photoluminescence are reported.  相似文献   

16.
19F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo6I Cl )F ]2?, n = 0–7, and Preparation of (TBA)2[(Mo6I )F ] The octa-μ3-iodo-hexafluoro-hexamolybdate(2?)ion [(Mo6I)F]2? is prepared for the first time. The system of the 21 innersphere mixed clusters (Mo6ICl)4+, n = 0–7 is formed by exchange of innersphere bound Cli against outersphere bound Ia on tempering solid [(Mo6Cl)I] at 400°C. Prolonged tempering leads to increasing average n values of the mixture, which is converted into the tetrabutylammonium salt (TBA)2[(Mo6ICl)F]. Using increments of chemical shifts and integral peak intensities the 54 19F-nmr signals of the 21 species (compound n = 8 is absent) are assigned and confirmed by the 2 D-19F/19F-COSY spectrum. From the measured intensities the distribution of the different compounds is determined and proves significant deviation from statistical occupation, revealing the preference of isomers with iodine atoms occupying edges of the innersphere cube and discrimination of those sharing diagonals of the faces. Moreover all compounds with n = 3 and 4 are present overaverage in comparison to the others.  相似文献   

17.
Vibrational Spectra of the Cluster Compounds (M6X12i) · 8H2O, M = Nb, Ta; Xi = Cl, Br; Xa = Cl, Br, I IR and, for the first time, Raman spectra at 80 K of the cluster compounds (M6X)X · 8H2O; M = Nb, Ta; Xi = Cl, Br; Xa = Cl, Br, I, have been recorded, characterized by typical frequencies of the (M6X) unit, which are only slightly influenced by the terminal Xa ligands. The most intense line with the depolarisation ≈? 0.2 in all Raman spectra is caused by inphase movement of all atoms and assigned to the symmetric metal-metal vibration v1, observed for the clusters (Nb6Cl) at 233–234, for (Nb6Br) at 186–187, for (Ta6Cl) at 199–203, and for (Ta6Br) at 176–179 cm?1. The IR spectra exhibit in the same series intense bands at 233, 204, 207, and 179 cm?1, assigned to the antisymmetric metal-metal vibration. The metal-metal frequencies are significantly higher than discussed before. The tantalum clusters show on excitation with the krypton line 647.1 nm in the region of a d–d transition at 645 nm a resonance Raman effect with series of overtones and combination bands. In case of (Ta6Br) another polarisized band is observed at 229 cm?1 and assigned to the Ta? Bri vibration v2. From the progressions of v1 and v2 anharmonicity constants of about ?3 cm?1 are calculated indicating a strong distortion of the potential curves.  相似文献   

18.
Aqueous sols of TiO2 (anatase, particle radius 25 Å) were excited with (347.1 nm)-laser light and the reaction of valence-band holes with halide ions (X = I?, Br?, Cl?) was investigated. Hole transfer takes place within the duration of the (10 ns)-laser pulse and results in the formation of anion radicals according to the sequence: The quantum yield of X increases in the order Cl < Br < I, attaining 0.8 for I at pH 1. It is affected by pH, halide concentration and the presence of a protective agent for the sol. RuO2 deposited onto TiO2 enhances markedly Cl and Br -formation, but has no effect on the yield of I. Laser-photolysis investigation of halide oxidation were also carried out with colloidal Fe2O3 (particle radius 600 Å). For I2?formation, the quantum yield exceeds 0.9 indicating almost quantitative hole scavenging by iodide.  相似文献   

19.
The kinetics of the reaction of CH3O with NO and the branching ratio for HCHO product formation, obtained as ΓHCHO = (Rate of HCHO formation) / (Rate of CH3O decay), have been studied using a discharge flow reactor. Laser induced fluorescence has been used to monitor the decay of the CH3O radical and the build-up of the HCHO product. Overall rate constants and product branching ratios were measured at room temperature over the pressure range of 0.72–8.5 torr He. Three reaction mechanisms were considered which differed in the routes of HCHO formation: (i) direct disproportionation; (ii) via an energized collision complex; or (iii) both reaction routes. It has been shown that data on the pressure dependence of the overall rate constant are not sufficient to distinguish between these mechanisms. In addition, an accurate value of Γ is required. Analysis of the available experimental data provided 0.0 and about 0.1 as the lower and upper limit for Γ, respectively. Since the rate constants derived for CH3ONO formation were not sensitive to the value assumed for Γ, k = (1.69 ± 0.69) × 10?29 cm6 molecule?2 s?1 and k = (2.45 ± 0.31) × 10?11 cm3 molecule?1 s?1 could be derived. The rate constant obtained for formaldehyde formation when extrapolated to zero pressure is k = (3.15 ± 0.92) × 10?12 cm3 molecule?1 s?1. © 1994 John Wiley & Sons, Inc.  相似文献   

20.
Dibromomethylsulfoniumsalts — Preparation and Crystal Structure The salts CH3SBrA? (A? = SbCl, AsF) were prepared by various routes and characterized by their Ramanspectra. CH3SBrAsF crystallized in the monoclinic space group P21/c with a = 770,5(4) pm, b = 942,4(12) pm, c = 1329,3(14) pm, β = 100,28(6)°, Z = 4. Distances and bond angles in the cation are as expected.  相似文献   

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