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1.
A.R. László Bursics Martin Murray F. Gordon A. Stone 《Journal of organometallic chemistry》1976,111(1):31-42
Bis(cyclopentadienyl)mercury readily undergoes Diels—Alder reactions with RCCR (R = CO2Me or CF3), CF3CFCFCF3, CF3CFCF2, (CF3)2CC(CN)2, C2(CN)4 and PhO to give stable adducts characterised by1H, 19F and 13C NMR, spectroscopy. Similar reactions of CF3CCCF3 and CF3CFCFCF3 with the cyclopentadiene derivatives Me3MC5H5 and (Me3M)2C5H4 (M = Si, Sn) are also described. 相似文献
2.
-N-Isopropylacetimidoyl chloride, CF3CClNCF(CF3)2, has been used as a precursor for a variety of heterocyclic and acyclic compounds. Reaction with azide ion yields a mixture of the imidoyl azide, CF3(N3)CNCF(CF3)2, and the 1,5-tetrazole, CF3CF(CF3)2. Hexafluoropropylideniminolithium produces as a minor product the conjugated diimine, (CF3)2CNC(CF3)NCF(CF3)2, from nucleophilic attack at the imidoyl chlorine and as a major product the triimine, (CF3)2CNC(CF3)NC(CF3)2NC(CF3)2, from further attack at the isopropyl fluorine. A thio-amide, CF3C(S)NHCH(CF3)2, and a Δ3-1,2,4-dithiazoline, (CF3)2, are produced upon reaction of hyrogen sulfide with the imidoyl chloride. Pathways are proposed for each of the reactions. 相似文献
3.
Ronald E. Banks Ismail M. Farhat Roy Fields Robin G. Pritchard Mohamad M. Saleh 《Journal of fluorine chemistry》1985,28(3):325-340
The nitrosoarenes ArNO (Ar = C6H5, 2-MeC6H4, 2,4,6- Me3C6H2 and C6F5) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds pyFN()Ar (pyF = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of pyFNNC6H2Me3-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound pyFN()C6F5. X-Ray methods have been used to determine the molecular geometry of pyFN()C6H2Me3-2,4,6. 相似文献
4.
Georg Grötsch Wolfgang Malisch Herbert Blau 《Journal of organometallic chemistry》1983,252(2):C19-C22
The reaction of the phosphonium metallates Me4P[C5R5(CO)(Me3P))R′] (M = W, R = H, R′ = Et (1a); M = Mo, R = Me, R′ = Me (1b)) with the silylating reagent Me3SiOSO2CF3 yields the neutral complexes C5R5(CO)(Me3P))R (2a, 2b) bearing a chelating O(2), C(4)-trimethylsiloxybutenone ligand. The structure of the new compounds is established by the IR, 1H and 31P NMR spectra. 相似文献
5.
In CF3CO2H solution, secondary ferrocenylcarbonium ions (FcHCR1R2R3) undergo a quantitative double-shift rearrangement to generate isomeric tertiary carbonium ions (FcR1CHR2R3). 相似文献
6.
Ronald E. Banks Neil Dickinson Alan P. Morrissey Adrian Richards 《Journal of fluorine chemistry》1984,26(1):87-92
Details are given for the preparation of heptafluoro-2-nitrosopropane and 1-chlorohexafluoro-2-nitrosopropane the routes CF3CFCF2 → [with CsFRFCO2Ag (RF = CF3, nC3F7)] (CF3)2CFAg → (with NOCl) (CF3)2CFNO and CF3CFCF2 → (with CsClNOCl) CF3(CF2Cl)CFNO, respectively, and for conversion of the latter nitroso-compound to chloropentafluoroacetone oxime reduction with aqueous potassium hydrogen sulphite. 相似文献
7.
The Raman, and infra-red spectra of Na+, K+, Rb+, Cs+, NH4+, C5H5NH+ and -Bu4N+ salts of the TeF5- ion are reported. They are assigned Cs symmetry. 19F n.m.r. spectra of the -Bu4N+ salt show J(Fax-Feq)50.4Hz, J(19Feq-125Te)1375.7Hz, J(19Fax-125Te)2883.3Hz and J(19Feq-123Te)1143.8Hz. No n.m.r. evidence was found for TeF62-. 相似文献
8.
Bis(dimethylamino)trifluoro sulfonium Salts: [CF3S(NMe2)2]+[Me3SiF2]‐, [CF3S(NMe2)2]+ [HF2]‐ and [CF3S(NMe2)2]+[CF3S]‐ From the reaction of CF3SF3 with an excess of Me2NSiMe3 [CF3(NMe2)2]+[Me3SiF2]‐ (CF3‐BAS‐fluoride) ( 5 ), from CF3SF3/CF3SSCF3 and Me2NSiMe3 [CF3S(NMe2)2]+‐ [CF3S]‐ ( 7 ) are isolated. Thermal decomposition of 5 gives [CF3S(NMe2)2]+ [HF2]‐ ( 6 ). Reaction pathways are discussed, the structures of 5 ‐ 7 are reported. 相似文献
9.
Gordon K. Anderson Ronald J. Cross Ljubica Manojlovic-Muir Kenneth W. Muir Tihomir Solomun 《Journal of organometallic chemistry》1979,170(3):385-397
The known complex, -(η-C5H5)2Rh2(CO)2(CF3C2CF3) is formed in high yield from (η-C5H5)Rh(CO)2 and CF3FCCF3 at 100°. The less stable -isomer of the complex is obtained in low yield from the same reaction. The infrared, 1H, 19F and 13C NMR spectra of the two isomers are compared. The -isomer undergoes CO scrambling in solution at room temperature, and the variable temperature 13C NMR spectra are consistent with a pairwise bridge opening and closing mechanism. The mechanism is extended to account for the isomerization of to isomer, whihc has a half-life of 12 h at room temperature. The 13C spectrum indicates that the -isomer is static in solution at room temperature. The -isomer is reversibly protonated by protonic acids, and BF4? and PF6? salts of the protonated species can be isolated. The spectroscopic properties of these salts are consistent with protonation at one of the alkynyl-carbons, but it is not possible to distinguish between two alternative structures for the complex cation.Treatment of (η-C5H5)2Rh2(CO)2(CF3C2CF3) with (η-C5H5)Rh(CO)2 gives the trinuclear complex (η-C5H5)3Rh3(CO)(CF3C2CF3) in 80% yield. The analogoug but-2-yne complex is formed from (η-C5H5)3Rh3(CO)3 and MeCCMe. The infrared, 1H, 19F and 13C NMR spectra indicate that the hexafluorobut-2-yne complex exists in two different structural arrangements in solution. One has an edge bridging, and the other a face bridging carbonyl. The proportion of the isomers is affected by the solvent polarity. The spectra of the but-2-yne complex indicate it is fluxional at room temperature, and has a face bridging structure in solution regardless of the polarity of the solvent. Reversible protonation of the hexafluorobut-2-yne complex occurs in protonic acids, and the salt [(η-C5H5)3Rh3(CO)(CF3C2CF3)H]+[BF4]?,H2O can be isolated. The spectroscopic properties of this complex are consistent with a structure incorporating an edge-bridging carbonyl, and probably, an edge-bridging hydride ligand. 相似文献
10.
The two perfluoro-azadienes CF2N.CRCF2 (R = CF3 or CF2Cl) show temperature dependent 19F n.m.r. spectra, with non-equivalent fluorine nuclei of the CF2N 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 FF coupling constants is much larger (. 24 Hz) than the remainder (0·5–5·5 Hz), possibly due to ‘through-space’ coupling of fluorines in the -skew conformation. 相似文献
11.
Different methods for the preparation of fluorinated iminium salts RR1CNR2R3+MF6? (R=R1=F ; R2=R3=CH3, C2H5 M=As, Sb 4a ? c R=H, R1=F; R2=R3=CH3 M=As, Sb 5a, b R=R1=CF3; R2=H, R3=CH3 M=Sb 12 R=R1=CF3; R2=R3=CH3 M=As 14) are reported, the spectroscopic properties (IR, NMR) of the cations of these salts are briefly discussed. By F?-addition to these salts, to 16, perfluoroalkyl-bis(alkyl)-amines ( (CF3)2CFN(CH3)2 15) can be prepared; from the methylation of CF3NCF2 bis(trifluoromethyl) methylamine (CF3)2NCH3 (11) was obtained. 相似文献
12.
F.Y. Petillon F. Le Floch-Perennou J.E. Guerchais D.W.A. Sharp Lj. Monojlovic-Muir K.W. Muir 《Journal of organometallic chemistry》1980,202(1):23-37
The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- Me], [Cp(OC)2Me], [CpW(CO)3C(CF3C(CF3)SMe], [CpW{η3-(O)}-(CO)2]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF3CCCF3 [CpMH(CO)3] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)3C(CF3)C(CF3)H]and an isomer of undetermined structure. 相似文献
13.
Ronald Eric Banks 《Journal of fluorine chemistry》1982,21(1):46
Mechanistic and synthetic highlights of out studies during the past twenty years on azides derived from fluorocarbon systems {alkenes ( CF3CFCFN3), aza-alkenes and -cycloalkenes [(CF3)N3], arenes ( C6F5N3), and heteroarenes( 4-N3.C5F4N)} will be discussed with emphasis on recent results bearing on the synthesis of novel seven-membered -heterocycles. 相似文献
14.
Contributions to the Chemistry of Halosilane Adducts. XVI. Synthesis, Properties, Crystal and Molecular Structure of Hexa(N,N-dimethylformamide)silicon(IV)-tetraiodide When SiI4 is reacted with DMF ionization of all SiI bonds occurs to give ( 2 ) (reaction of pure components) or ( 1 ) (CHCl3 solution). IR and 1H-NMR spectra are in accordance with the formation of the octahedral cation [Si · 6 DMF]4+, DMF being coordinated through the CO group. 1 is only slowly attacted by methanol or water DMF being liberated. 1 crystallizes in the monoclinic space group C2/c with 4 formula units per unit cell. The cation [Si · 6 DMF]4+ has 1 symmetry. DMF is coordinated to Si in trans-configuration with respect to NMe2 with donation by oxygen. SiO bond distances (175.4–177.2 pm) correspond to those of [Si(O2C6H4)3]2? and [Si(acac)3]+; an increase of the CO distances (126.1–128.9 pm) and decrease of the CN distances (126.4–129.1 pm) as compared to free DMF is observed. These changes and structural data are discussed. 相似文献
15.
The perfluoronitrosocycloalkanes, heptafluoronitrosocyclobutane and nonafluoronitrosocyclopentane, are convenient precursors to a family of new perfluorocycloalkyl(aryl) diazenes. With aniline and o-aminobenzamide, FNNH and FNNC(O)NH2 (x = 2,3) are formed. Additionally, heptafluoronitrosocyclobutane gives FNNF and FNNNH2 with 2,3,5,6-tetrafluoroaniline and o-phenylenediamine 相似文献
16.
Robert S.-C. Tsai Gerald L. Larson Alfonso Oliva 《Journal of mass spectrometry : JMS》1979,14(7):364-368
The mass spectra of a series of β-ketosilanes, p-Y? C6H4Me2SiCH2C(O)Me and their isomeric silyl enol ethers, p-Y? C6H4Me2SiOC(CH3)?CH2, where Y = H, Me, MeO, Cl, F and CF3, have been recorded. The fragmentation patterns for the β-ketosilanes are very similar to those of their silyl enol ether counterparts. The seven major primary fragment ions are [M? Me·]+, [M? C6H4Y·]+, [M? Me2SiO]+˙, [M? C3H4]+˙, [M? HC?CCF3]+˙, [Me2SiOH]+˙ and [C3H6O]+˙ Apparently, upon electron bombardment the β-ketosilanes must undergo rearrangement to an ion structure very similar to that of the ionized silyl enol ethers followed by unimolecular ion decompositions. Substitutions on the benzene ring show a significant effect on the formation of the ions [M? Me2SiO]+˙ and [Me2SiOH]+˙, electron donating groups favoring the former and electron withdrawing groups favoring the latter. The mass spectral fragmentation pathways were identified by observing metastable peaks, metastable ion mass spectra and ion kinetic energy spectra. 相似文献
17.
Augusto De Renzi Achille Panunzi Michaelangelo Scalone Aldo Vitagliano 《Journal of organometallic chemistry》1980,192(1):129-132
Amination of PtII-allene complexes of the type cis[PtCl2(Me2CCCHR)(PPh3)] gives the new four-membered C, N chelate aminoalkenyl complexes [Me2(PPh3)Cl]. These undergo ready insertion of carbon monoxide into the CPt σ-bond; the resulting acyl complexes are oxidized by hydrogen peroxide to aminoacidato complexes, and the free unsaturated β-aminoacids can be recovered in good yield by ligand displacement. 相似文献
18.
Ionic trifluoromethanesulphonates (triflates) are strongly solvated with their conjugate acid in dichloromethane (Ph3C+, n-Bu4N+, Ag+) and acetonitrile (Na+, Ag+). A 1H and 19F NMR study of the chemical shifts of various acid-salt mixtures show that in CH2Cl2 three homoconjugates A? · HA, A?. (HA)2 and A?(HA)3 were formed with large formation constants whereas in acctonitrile only the 1:1 homoconjugate was formed with an equilibrium constant K1 ~ 4 1 · M?1. This result explains why the protonation by CF3SO3H of non-polymerizable olefins such as 1,1-diphenylethylene and 3-phenylindene is always incomplete ( and respectively) in CH2Cl2. Conditions in which covalent triflates could be obtained have been investigated. As a consequence of homoconjugation, reaction of Ph3COH with triflic anhydride led to Ph3C+ CF3SO?3 HOSO2CF3. Other tertiary alcohols were dehydrated by triflic anhydride and led to ethylenic compounds (1,1-diphenylethanol) or ethers (2-phenyl 2-propanol). Esters were only observed in the case of benzyltriflate (at ?20°) and in the case of 1-phenylethyltriflate which is a model of polystyryltriflate (stable at room temperature). 相似文献
19.
Synthesis, Structure, and Reactivity of the Ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2] Reaction of equimolar amounts of the carbenium iodide [Me2N(Ph)CSMe]I and LiAs(SiMe3)2 · 1.5 THF afforded the thermolabile arsaalkene Me3SiAs = C(Ph)NMe2 ( 1 ), which in situ was converted into the black crystalline ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2)] ( 2 ) by treatment with [(η5‐C5Me5)(CO)2FeCl]. Compound 2 was protonated by ethereal HBF4 to yield [(η5‐C5Me5)(CO)2FeAs(H)C(Ph)NMe2]BF4 ( 3 ) and methylated by CF3SO3Me to give [(η5‐C5Me5)(CO)2FeAs(Me)C(Ph)NMe2]‐ SO3CF3 ( 4 ). [(η5‐C5Me5)(CO)2FeAs[M(CO)n]C(Ph)NMe2] ( 5 : [M(CO)n] = [Fe(CO)4]; 6 : [Cr(CO)5]) were isolated from the reaction of 2 with [Fe2(CO)9] or [{(Z)‐cyclooctene}Cr(CO)5], respectively. Compounds 2 – 6 were characterized by means of elemental analyses and spectroscopy (IR, 1H, 13C{1H}‐NMR). The molecular structure of 2 was determined by X‐ray diffraction analysis. 相似文献
20.
Reactions of HgCl2 with η5-C5H5Fe(CO)2R (R CH2CHCH2 and CH2C(CH3)CH2) in THF at 25°C rapidly afford adducts of the two reactants. These adducts were converted to the corresponding PF6? salts, [η5-C5H5Fe(CO)2(η2-CH2C(R)CH2HgCl)]+ PF6? (R H and CH3), for characterization. Slower reactions with cleavage of the ironcarbon σ bond and elimination of the R group from η5-C5H5Fe(CO)2R occur for R CH2CHC(CH3)2, CH2CHCHC6H5, and CH2CCC6H5. Both elimination and adduct formation are observed when R CH2CHCHCH3. The kinetics of the cleavage reactions are presented and possible mechanisms for both cleavage and adduct formation are discussed. 相似文献