共查询到20条相似文献,搜索用时 31 毫秒
1.
G.R. Clark C.M. Cochrane W.R. Roper L.J. Wright 《Journal of organometallic chemistry》1980,199(2):C35-C38
The osmium carbyne complex, Os(CR)Cl(CO)(PPh3)2, (R p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, and [R)Cl(CO)(MeCN)(PPh3)2] ClO4 X-ray crystal structure determination of R)Cl(CO)(PPh3)2 confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand. 相似文献
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3.
Methods of substituting pyridine by perhalogenomethylmercapto groups are discussed. The side chain chlorination of 2-(methylmercapto)pyridine leads gradually to 2-(trichloromethylmercapto)pyridine hydrochloride () and 2-(trichloromethylmercapto)pyridine (). Neither a direct reaction of pyridine with CF3SCl nor the way over a Grignard reaction or a sulfenylcarboxylate lead to CF3S-substituted products. Reactions of pyridine and bromopyridines with Hg(SCF3)2 yield 1:1-adducts () only. Lithium tetrakis(1,2-dihydro-1-pyridyl)aluminate (LDPA) reacts with CF3SCl to give 3-(trifluoromethylmercapto)pyridine (); in addition a disubstituted product can be identified massspectroscopically. 1H- and 19F-NMR-spectra are reported. 相似文献
4.
C. Glidewell G.S. Harris H.D. Holden D.C. Liles J.S. McKechnie 《Journal of fluorine chemistry》1981,18(2):143-154
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, 21/, = 12.926(4), = 17.819(6), = 14.994(4) Å, β = 98.97(3)°, Z = 4. The structure contains cations [(Ph3AsO)2H]+ in which O is 2.44(2)Å, and anions BF4?. 相似文献
5.
《Polyhedron》2001,20(9-10):1089-1095
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The superoxo complex [Co(CN)5O2]3- was found to act as a reducing agent towards quinones. One-electron reduction took place with -quinones whereas two-electrons reduction with -quinones. 3,5-Di--butyl--benzoquinone gave the corresponding semiquinone Co(III) complex quantitatively. 相似文献
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The synthesis of diketones , and starting from diene by photochemical cyclization followed by RuO4 oxidation is described and stereochemistry of products is proposed. 相似文献
8.
Reaction of the amines (CF3)2NX (X=Cl,Br) with norbornadiene either in solvent (CH2Cl2) at ?78 °C in the dark or in the vapour phase at 20 °C in daylight gives a mixture of 3-halogeno-5-(-bistrifluoromethylamino)nortricyclene (, -and , -isomers) and -5-(-bistrifluoromethylamino)- -7-halogenonorbornene in quantitative yield formed halonium ion addition to the diene. The reaction of the amine (CF3)2NBr in solvent Me2O or Et2O at ?78 °C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene (, - and , -isomers) and the amine (CF3)2NR (R=Me, Et) in high yield. 相似文献
9.
Halogen cleavage reactions of -(-PhCHDCHD)Mn(CO)4, PEt3 () are studied in detail and are found to proceed either predominantly with retention or inversion, or non-stereospecifically, depending on reaction conditions. Reaction mechanisms involving SE2 (inversion), SE2 (retention) and SE (oxidative) processes are proposed, demonstrating that halogen cleavage reactions of straddle the mechanistic borderline between electrophilic substitution and oxidation processes of transition metal alkyl compounds. 相似文献
10.
The reaction of Pt(PPh3)4 with CH2Cl1 in benzene yields the cationic ylide complex -[Pt(PPh3)2(CH2PPh3)Cl]I in high yield. This complex has been converted to -[(PPh3)2(CH2PPh3)X]X (X Br or I) by reaction with LiBr or NaI. Reaction of -[Pt(PPH3)I]I with iodine yields -[Pt(PPh3)2(CH2PPh3)I]I3. Nmr data are given in support of the suggested structures. 相似文献
11.
The diene reacted with CHCl3/aq. NaOH/PTC in CH2 Cl2 unexpectedly to give a mixture of the chlorination products and . Usual chlorination with Cl2 yielded similarly , , and dependent on the amount of Cl2. The formation of as well as the reaction of to give (besides ) shows an unusual Cl-Cl-interaction. 相似文献
12.
The structure of [Pt2Cl(CO) (μ-Ph2PCH2PPh2)2] [PF6] was determined by -ray methods and refined to = 0.082, using diffractometric intensities of 5646 independent reflections. The crystals are monoclinic, space group 21/, = 12.919(3), = 15.576(6), = 25.151(5)Å, β = 94.82(3)°, = 4. They are built of octahedral hexafluorophosphate anions and dinuclear platinum(I) cations. The latter contain PtCl and PtCO fragments linked to one another by a PtPt 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: PtPt 2.620(1), PtCl 2.384(5), PtC 1.89(3) and PtP 2.291(5) – 2.308(5)Å. 相似文献
13.
Gábor Blaskó Natesan Murugesan Alan J. Freyer Daniella J. Gula Bilge Şener Maurice Shamma 《Tetrahedron letters》1981,22(33):3139-3142
Stereoselective rearrangement of indenobenzazepine cis ketols and with TPAA in pyridine produces spirobenzylisoquinolines and , respectively. The latter product is also obtained by rearrangement of trans ketol . The transformation of ketols and must, therefore, proceed through the intermediacy of aziridinium cation . A similar process obtains in the transformation of to . NaBH4 reduction of gives (±)-raddeanine (). Rearrangement of diol supplies directly. (±)-Yenhusomine () is obtained from the reamangement of either diol, or . In like fashion, diols and supply spirobenzylisoquinoline . 相似文献
14.
The Functionalized Grignard reagent reacts with allylic chloride , in the presence of Li2CuCl4, to provide lactarol-THP ether which is subsequently converted to (±)-lactaral in 72% overall yield from . 相似文献
15.
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
16.
A synthesis of the thromboxane A2 analog, -(9,11) ,(11,12)-dideoxa-(9,11)-methylene-(11,12)-epithio-thromboxane A2 methyl ester , is described. 相似文献
17.
The extraction of Co(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one ((H)PMBP) and tri-n-octylamine (TOA) is investigated in order to explore the influence of diluents and inorganic anions with synergistic acidic extractant + liquid anion exchanger systems. Although it is proved that the same species [HTOA]+ [Co(PMBP)3]? is extracted from various inorganic media, with toluene as the diluent, the presence of ClO4? SO42? or Cl? anion modifies the distribution of the anions which are associated to (HTOA)+ in the organic phase, leading to different synergistic equilibria; with Cl? or SO42?: + ,PMBP?) ?,Co(PMBP)3? (log K = 6.10) and with ClO4? : + + ,ClO4? ? ,Co(PMBP)3? + H+ + ClO4? (log K = 2.34) The same synergistic equilibrium is observed for the extraction of Ni(II) from ClO4? medium, with a comparable value of the constant (log K = 2.45). The synergistic effect is cancelled in n-octanol. 相似文献
18.
Pierfrancesco Bravo Giovanni Fronza Calimero Ticozzi Giorgio Gaudiano 《Journal of organometallic chemistry》1974,74(1):143-154
Keto-stabilized sulphonium ylides displace styrene and benzonitrile from their adducts with PdCl2 to give stable ylidePdCl2 complexes. Evidence is given for epimeric equilibrium between trans square-planar structures of these new complexes in solution.A ylidePdI2 complex, obtained from dimethylsulphonium methylide, is also described. 相似文献
19.
Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O(CH3) and i-C3F7N(CH3 with symdimethylethylenediamine (1). In contrast, CF3C(O)NSF2 and (Rf)2SF2 (Rf = CF3, i-C3F7 form only acyclic compounds, CF3C(O)N(CH3)CH2CH2N(CH3)C(O)CF3 and RfSN(CH3)CH2CH2N(CH3)SRf with (1). With PF3, PF5 and OPF3, cyclic compounds F, F3, and -(O)F result. When the latter two compounds are reacted further with LiNC(CF3)2, N(CH3)CH2CH2N(CH3)PF2NC(CF3)2 and (O)NC(CF3)2) form. 相似文献
20.
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 21/, = 10.01(2), = 19.33(3), = 8.40(1) Å, β = 82.27(6)°; final R = 0.044. 相似文献