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1.
Reaction of [Ru3(CO)12 with (CF3)2P---P(CF3)2 in p-xylene at 140°C yielded the compounds [Ru4(CO)13{μ-P(CF3)2}2] (1), [Ru4(CO)14{μ-P(CF3)2}2] (2) and [Ru4(CO)11{μ-P(CF3)2}4] (3). Reaction with [(μ-H)4Ru4(CO)12] under similar conditions yielded [(μ-H)3Ru4(CO)12{μ-P(CF3)2}] (4). All four compounds have been characterised by X-ray crystallography. The fluxional behaviour of the hydrides in 4 has also been studied by variable-temperature NMR spectroscopy. Compounds 1, 2 and 4 were also obtained from the reactions of Ru3(CO)12 with (CF3)2PH in dichloromethane at 80°C.  相似文献   

2.
1,3,3-Trimethyl-3,4-dihydroisoquinolines react with 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene to give 4-amino-6,6-dimethyl-2,2-bis(trifluoromethyl)-3-cyano-6,7-dihydro-2H-benzo[a]quinolizines. The reaction of 3,3-dimethyl-1-cyanomethylidene-1,2,3,4-tetrahydroisoquinoline and the methyl ester of 3,3-dicyano-2-(trifluoromethyl)acrylic acid leads to 5,5-dimethyl-3-oxo-2-(trifluoromethyl)-2-(dicyanomethyl)-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinoline.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1888–1892, August, 1992.  相似文献   

3.
在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni2L2(bib)2·2H2O]·5H2O}n(1), [Ni2L2(bpy)]n(2)和{[Ni2L2(bibpip)2·2H2O]·6H2O}n(3)[H2L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、 红外光谱、 元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{42·65·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{48·54·63}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P1ˉ空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{44·62}拓扑结构.  相似文献   

4.
Sodium bis(trimethylstannyl)amide NaN(SnMe3)2, isolated by the reaction of trimethylstannyldiethylamine with sodium amide, reacts with tris(trimethylsilyl)hydrazino—dichloro-phosphine to form bis(trimethylsilyl)bis(trimethylstannyl)-2-phospha-2-tetrazene, (Me3Si)2N-N=P-N(SnMe3)2. Both the molecules have been isolated and characterized.  相似文献   

5.
The coordinating properties of the trifluoromethyl elemental compounds Me2PP(CF3)2 and Me2AsP(CF3)2 have been studied by the synthesis and spectroscopic investigations (IR, NMR, MS) of their complexes cis-M(CO)4L2 (A), [(CO)4ML]2 (B) and [(CO)5M]2L (C) (M = Cr, Mo, W). Complexes of type A with L = Me2PP(CF3)2 are obtained in good yield by reaction with M(CO)4NBD (NBD = norbornadiene), whereas with L = Me2AsP(CF3)2 the homobinuclear compounds B are formed. The attempt to prepare the cis-M(CO)4[Me2AsP(CF3)2]2 complexes by treating M(CO)4(Me2AsH)2 with P2(CF3)4 is successful only for M = W. Binuclear compounds of type B or C, in general, can be prepared by stepwise reaction of the ligands with either M(CO)4NBD or M(CO)5THF.  相似文献   

6.
It was demonstrated that the outcome of the reaction of hexafluoropropene, sulfur and vinyl ether strongly depends on the catalyst and reaction conditions. The reaction of HFP and Sx leading to the formation of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1) when it is catalyzed by CsF, proceeds under milder conditions and is easier to control compared to KF catalyzed process. The order of addition of reagents plays a crucial role on the outcome of the reaction. For example, the addition of vinyl ether to pregenerated solution of 1 in DMF solvent results in slow reaction, leading to the corresponding 2,2-bis(trifluoromethyl)-4-R-thietanes in 8-91% yield, and it is catalyzed by either by KF or CsF. The addition of second mole of sulfur to the solution of 2,2-bis(trifluoromethyl)-4-R-thietanes in the presence MF catalyst leads to insertion of sulfur into thietane ring with the formation of the corresponding cyclic disulfides—3,3-bis(trifluoromethyl)-5-R-1,2-dithietanes. On the other hand, the addition of second mole of sulfur to the solution of 1 in DMF in the presence of CsF catalyst, followed by addition of vinyl ether results in exothermic reaction, and it produces the corresponding 2,2-bis(trifluoromethyl)-4-alkoxy-1,3-dithiolanes in good yield.It was also demonstrated that 2,2-bis(trifluoromethyl)-4-R-thietanes can undergo disproportionation under action of fluoride anion, producing a mixture of the corresponding 1,2-dithiolane and CF2C(CF3)CH2CFHOR. The nucleophilic attack of fluoride anion in this case proceeds selectively on the carbon of the thietane ring, bearing alkoxy group.The structure of 2,2-bis(trifluoromethyl)-4-R-thietanes forming as the result of 2 + 2 cycloaddition reaction between hexafluorothioacetone generated “in situ” from dimer 1 and vinyl ether was firmly supported by single crystal X-ray diffraction data, obtained for thietane bearing t-BuO-group.  相似文献   

7.
The attempted preparation of bis(trifluoromethylsulphanyl)thioketene is described. Mono-and di-(trifluoromethylsulphanyl)-substituted orthothioesters may be prepared fromCH3C(SC2H5)3 and CF3SCl in the presence of anhydrous ZnCl2. The unstable compoundshave been isolated and characterized. The corresponding CF3Se and CF3SO2 derivativesare only formed as intermediates which decompose to ketene diethylmercaptal. Suchmono- and di-substituted products are obtained in good yield from H2C=C(SC2H5)2 andCF3ECl (E=S, Se). The reaction of H2C=C(SC2H5)2 with CF3SO2F gave only poor yieldsof (CF3SO2)nCH2−n=C(SC2H5)2 (n=1, 2) which were only capable of characterizationin etheral solution by spectral means. Attempts to prepare (CF3S)2C=C=S by refluxing(CF3S)2CHC(O)Cl, (CF3S)2CHC(O)OH or (CF3S)2C=C=O with P4S10 in toluene yieldedonly the cyclic dimer and the corresponding 1,3,4-trithiolan.  相似文献   

8.
Hexa-alkylphosphorus triamides and trifluoromethyl bromide react to give trifluoromethyltris(dialkylamino)phosphonium bromides which were used for the trifluoromethylation of benzaldehyde and copper(I) iodide in the presence of fluoride anions with different counterions; tris(diethylamino)difluorophosphorane proved to be a masked fluoride anion donor. The structures of [CF3P(NMe2)3]+Br and [CF3P(NEt2)3]+Br have been determined by single-crystal X-ray investigations and shown to exhibit a distorted tetrahedral bond configuration with a rather long (F3)C---P bond of 1.866(9) or 1.896(6) Å, respectively.  相似文献   

9.
The reactions of MnRe(CO)10 with As2(CF3)4 and MnCo(CO)9 with P2(CF3)4, As2(CF3)4, S2(CF3)2, Se2(CF3)2, (CF3)2EI (E = P, As), (CF3)2AsH, (CF3)2AsE′CF3 (E′ = S, Se), (CF3)2PSeCF3, Me2AsI and (CF3)2PPMe2, respectively, have been studied under various conditions. Besides already known mono- and binuclear compounds the heteronuclear complexes MnRe(CO)8[As(CF3)2]2 and MnCo(CO)7[E(CF3)2]2 (E = P, As) are formed. The reactions proceed via cleavage of the M---M′ bond and formation of the mononuclear species Mn(CO)5X and M′(CO)nY (M′ = Re, n = 5; M′ = Co, n = 4).  相似文献   

10.
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF3SO2)2O) and SCSC≈ 150° ((CF3SO2)2CF2 are lowest in energy. According to the GED analyses the dominant conformer of (CF3SO2)2O2 possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF3SO2)2CF2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.  相似文献   

11.
以苯基嘧啶/吡啶基嘧啶为母核, 同时引入2个三氟甲基(CF3)合成了2-[3,5-二(三氟甲基)苯基]-5-氟基嘧啶(tfmphfppm)和2-[2,6-二(三氟甲基)-4-吡啶基]-5-氟基嘧啶(tfmpyfppm)主配体, 并以2-(5-苯基-1,3,4-噁二唑-2-)苯酚(pop)为辅助配体合成了2种铱(III)配合物Ir(tfmphfppm)2(pop)和Ir(tfmpyfppm)2(pop), 其发射光谱峰分别位于484和504 nm, 分别属于蓝绿光和绿光发射, 发光量子效率分别达到76%和89%. 由于氮杂环和2,5-二苯基-1,3,4-噁二唑基团的存在, 配合物具有较低的最低未占据分子轨道(LUMO)能级和较高的电子迁移率. 以2种 铱(III)配合物为发光中心制备的有机电致发光器件(OLED)显示了较好的器件性能, 其最大亮度(Lmax)、 最大电流效率(ηc, max)、 最大功率效率(ηp, max)和最大外量子效率(EQEmax)分别为33379 cd/m2, 76.55 cd/A, 31.59 lm/W和26.7%; 并且该器件显示了比较小的效率滚降, 在亮度为1000 cd/m2时, 器件的ηc仍然可以达到72.71 cd/A. 本文结果表明, 氮杂环、 2,5-二苯基-1,3,4-噁二唑和三氟甲基基团可以有效提高铱(Ⅲ)配合物的发光性能和电子迁移率, 从而提高器件的性能.  相似文献   

12.
Sodium dithionite initiated addition of CF2Br2, CF3I and (CF3)2CFI to the terminal double bond of allylbenzenes and of (CF3)2CFI to allylpyridines in a MeCN/H2O system were investigated. The reactions of CF2Br2 with allylbenzenes gave comparable amounts of adducts, 1-(2,4-dibromo-4,4-difluorobutyl)benzenes, debrominated products,1-(4-bromo-4,4-difluorobutyl)benzenes, and dimeric compounds in total yields 40-66%. Treatment of the adducts with DBU resulted in double dehydrohalogenation affording 4-aryl-1,1-difluorobutadienes which undergo Diels-Alder condensation with nitrogen dienophiles to give N-heterocycles with difluoromethylene group in the ring. The reactions of CF3I and (CF3)2CFI with allylbenzenes gave the respective adducts, (4,4,4-trifluoro-2-iodobutyl)benzenes and 1-(4,5,5,5-tetrafluoro-4-(trifluoromethyl)-2-iodopentyl)benzenes as the main products. Dehydrohalogenation of these adducts resulted, respectively, in (4,4,4-trifluoro-but-1-enyl)benzenes and 4-aryl-1,1-bis(trifluoromethyl)butadienes in high yields. (CF3)2CFI reacted rapidly with allylpyridines to give mixtures from which, after treatment with DBU, 4-pyridyl-1,1-bis(trifluoromethyl)butadienes were isolated in a ca. 60% yield.  相似文献   

13.
Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF3(CF2)7(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)7CF3, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF3(CF2)5(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)5CF3, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF3(CF2)3(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)3CF3, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured.  相似文献   

14.
席夫碱配体由于在合成上具有极大的灵活性和良好的配位能力 ,因而席夫碱 -金属配合物的研究一直受到广泛重视 .多年来 ,席夫碱配体由简单的单齿发展到多齿和大环配体 .此外 ,过渡金属的席夫碱配合物具有独特的结构、性能和广泛的应用 ,如氧化还原 [1] 、催化 [2 ] 以及生物体系的化学模拟 [3 ] ;另一方面 ,由于银原子配位方式的多样性 (二、三、四和五配位 ) ,便于人们对超分子化合物的组装规律进行系统研究 ,因而银配合物的研究正日益引起人们极大的兴趣 [4~ 7] .鉴于此 ,我们设计合成了一个新的四齿席夫碱配体 L ,研究了其与 CF3 SO3 …  相似文献   

15.
Complexes of 2,3-bis(4,5-dimethylthio-1,3-dithiole-2-ylidene)succinonitrile (L) with AgX salts have been prepared and fully characterized by elemental analysis, IR and single-crystal X-ray analysis. The structural topology in the solid state is found to depend on the type of counterions. With AgNO3, a 3D coordination network of composition [Ag2(L)(NO3)2]n (1) forms in which Ag(I) is six-coordinated, bonding to two sulfur atoms of ligand L, a neighboring ligand nitrogen atom and totally three oxygen atoms of bridging nitrate anions. Changing the counterion to triflate produces a 2D coordination network of composition [Ag2(L)(CF3SO3)2]n (2) in which Ag(I) is five-coordinated and bonds to two sulfur atoms of ligand L and totally three oxygen atoms of bridging triflate anions. Obviously, in the latter case, the nitrile groups of L are non-coordinating.  相似文献   

16.
Four novel tetranuclear macrocyclic complexes of the formula [(CuLi)3Fe](ClO4)3·3H2O (i=1–4, Li are the dianions of the [14]N4 and [15]N4 macrocyclic oxamides, namely 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene, 2,3-dioxo-5,6:13,14-dibenzo-9-methyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene and 2,3-dioxo-5,6:14,15-dibenzo-7,13-bis(ethoxycarbonyl)-1,4,8,12-tetraazacyclotetradeca-7,12-diene] have been prepared and characterized. These complexes are the first examples of oxamido-bridged Cu(II)–Fe(III) heterometallic species. Cryomagnetic studies on [(CuL1)3Fe](ClO4)3·3H2O (1) and [(CuL3)3Fe](ClO4)3·3H2O (3) (77–300 K) revealed that the Cu(II) and Fe(III) ions interact antiferromagnetically through the oxamido bridge, with the exchange integral J=−30.8 cm−1 for 1 and J=−28.7 cm−1 for 3 based on . The interaction parameters have been compared with that of the related [Cu3Mn] compound.  相似文献   

17.
The comparative reaction chemistry between first and second derivative paraelement analogs ( (CF3)2PH, (CF3S)2PH, CF3SH, CF3SSH, CF3SNH2, (CF3S)2NH, (CF3S) 3N) and F-N-isopropylacetimidoyl chloride [CF3CCl=NCF(CF3)2, I] has been investigated. Reaction schemes are presented. The reactions of I with NH3 and NaI are also reported. Analytical data is provided for previously unreported compounds along with more detailed analysis of known compounds.  相似文献   

18.
A coordination polymer formulated as {[Mn2L(N3)4]·2H2O)n(1) [L = 1,4-bis(pyridinil-3-carboxylato)-1,4- dimethylbenzene] was synthesized and structurally and magnetically characterized. The uniform Mn(Ⅱ) chains with mixed (μ-EO-N3)2(μ-COO) triple bridges (EO = end-on) are linked by L ligands to generate a 2-fold interpenetrating 3D framework. Meanwhile, magnetism analysis reveals antiferromagnetic coupling for 1.  相似文献   

19.
The reaction of Pt(PPh3)n (n = 3 or 4) with [(CF3)3Ge]2Hg or (CF3)3GeHgPt(PPh3)2Ge(CF3)3 (I) gives a stable diplatinum complex [(CF3)3GePt(PPh3)2]2Hg (II). X-Ray analysis has established that compound II contains a Ge---Pt---Hg---Pt---Ge chain of C2 symmetry. Both of the Pt atoms have distorted square-planar coordinations. The bond lengths are: Pt---Hg, 2.630(2) and 2.665(2) Å; Ge---Pt, 2.410(4) and 2.407(4) Å.

Compound II reacts with dihydrogen in THF solution under mild conditions to give mercury and the hydride (CF3)3GePt(PPh3)2H. On interaction of II with R2Hg organomercurials (R = Cl, Et, GeEt3, Ge(CF3)3, Ge(C6F5)3) an unknown reaction takes place: Pt(PPh3)2 moieties migrate from the polymetallic grouping into the substrate with the formation of the corresponding RHgPt(PPh3)2R complexes or their demercuration products, R2Pt(PPh3);, (R = Cl, Et). The latter react further with complex I formed in the first step of the process to give Hg and (CF3)3GePt(PPh3)2R. The reaction schemes are discussed.  相似文献   


20.
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF3SO2)2O) and SCSC ≈ 150° ((CF3SO2)2CF2) are lowest in energy. According to the GED analyses the dominant conformer of (CF3SO2)2O possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF3SO2)2CF2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.  相似文献   

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