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1.
We report metathetical reactions of IF5 with series of α,β-trimethylsilylated ethanediolates with increasing numbers of CH3-groups in α- and β-positions. Short lived intermediates IF4[OC2H4?n(CH3)nO]X with X = Si(CH3)3 or IF4 and stable chelates IF3[OC2H4?n(CH3)nO] and IF[OC2H4?n(CH3)nO]2 (n = 0–4) are observed and characterized. Time and temperature dependence of 19F-NMR-spectra in relation to degree of methylation, arrangement and stereo-chemistry are discussed referring to previously published mono- and polynuclear I(V)-compounds containing a series of monodentate alcoholates CH3?n(CH3)nO? and (CH3)3CCH2O? (n = 0,2,3) [1,2] and of bidentate alcoholates ?O(CH2)nO? (n = 2,3,4,5,6,12) [1]. In contrast to aliphatic α,β-diolates the aromatic diolates 1,2-C6H4(O?)2, 1,2-C6Cl4(O?)2 rapidly undergo redox reactions even at low temperatures.  相似文献   

2.
The reaction of niobium pentachloride with three equivalents of 2-t-butylphenol in carbon tetrachloride afforded [NbCl2(OC6H4C(CH3)3-2)3]. The identity of the complex has been established by elemental analyses, molar conductance, molecular weight determination, IR, 1H, and 13C-NMR and UV-Vis spectral studies. Based upon these studies, a square–pyramidal geometry around niobium has been proposed. Thermal behavior of the complex has been studied by TGA and DTA. Acceptor behavior of [NbCl2(OC6H4C(CH3)3-2)3] toward Ph3P, Ph3As, Ph3PO, Ph3AsO, and an uncommon ligand arsenictrithiophenoxide As(SPh)3 allows the isolation of 1 : 1 addition compounds as shown by physicochemical, IR, and 1H-NMR spectral studies. The formation of [NbCl2(OC6H4C(CH3)3-2)3] · As(SPh)3 appears to be the first adduct of its class and suggests the suitability of As(SPh)3 as a ligand.  相似文献   

3.
《Polyhedron》2002,21(9-10):909-915
The series of complexes [N3P3(OC6H5)5OC6H4CH2CN·MCln]PF6, N3P3(OC6H4CH2CN)6·(MCln)6](PF6)6, [N3P3(OC6H5)5OC6H4CH2CN·MCln−1]Cl and [N3P3(OC6H4CH2CN)6·(MCln−1)6]Cl6, MCln=MnCl2, FeCl3, CoCl2, NiCl2, CuCl2 have been synthesized by reaction of the corresponding cyclophosphazene ligands: N3P3(OC6H5)5OC6H4CH2CN (L1) and N3P3(OC6H4CH2CN)6 (L2) with the respective salts MCln in CH3OH as solvent and in presence or absence of NH4PF6. The new compounds were characterized by elemental analysis and IR, UV–Vis and EPR spectroscopy as well as electrochemical methods. The reaction of CuCl2 with the ligand L1 affords the copper (I) complex. [N3P3(OC6H5)5OC6H4CH2CN·Cu]PF6 instead the expected Cu(II) complex, which was characterized by multinuclear NMR. For comparison, the complex [N3P3(OC6H5)5OC6H4CH2CN·ZnCl]PF6 was also prepared. The hexametalladendrimers of iron exhibits a six-electron reduction while that the correspondent monometalladendrimers exhibit a single one-electron reduction. Upon coordination νCN increase in a similar way to crystal field effects dependence with the metal.  相似文献   

4.
Interesting varieties of heterobimetallic mixed-ligand complexes [Zr{M(OPri) n }2 (L)] (where M = Al, n = 4, L = OC6H4CH = NCH2CH2O (1); M = Nb, n = 6, L = OC6H4CH = NCH2CH2O (2); M = Al, n = 4, L = OC10H6CH = NCH2CH2O (3); M = Nb, n = 6, L = OC10H6CH = NCH2CH2O (4)), [Zr{Al(OPri)4}2Cl(OAr)] (where Ar = C6H3Me2-2,5 (5); Ar = C6H2Me-4-Bu2-2,6 (6), [Zr{Al(OPri)4}2(OAr)2] (where Ar = C6H3Me2-2,5 (7); Ar = C6H2Me-4-Bu2-2,6 (8), [Zr{Al(OPri)4}3(OAr)] (where Ar = C6H3Me2-2,5 (9); Ar = C6H3Me2-2,6 (10), [ZrAl(OPri)7-n (ON=CMe2) n ] (where n = 4 (11); n = 7 (12), [ZrAl2(OPri)10-n (ON=CMe2) n ] (where n = 4 (13); n = 6 (14); n = 10 (15) and [Zr{Al(OPri)4}2{ON=CMe(R)} n Cl2–n] [where n = 1, R = Me (16); n = 2, R = Me (17); n = 1, R = Et (18); n = 2, R = Et (19)] have been prepared either by the salt elimination method or by alkoxide-ligand exchange. All of these heterobimetallic complexes have been characterized by elemental analyses, molecular weight measurements, and spectroscopic (I.r., 1H-, and 27Al- n.m.r.) studies.  相似文献   

5.
Reactions of Undecacarbonyl(acetonitrile)triiron with Alkyne Ethers (CO)11(CH3CN) 1 reacts with the alkyne ethers H3C? C?C? OC2H5 2a , H? C?C? OC2H5 2b , H3C? O? CH2? C?C? CH2? O? CH3, 2c and H3C? O? C(CH3)H? C?C? C(CH3)H? O? CH3 2d forming different cluster products depending on the substituents and the reaction conditions. The product obtained with 2a is the bisalkylidyne cluster Fe3(CO)9(m?3-C? CH3)(m?3-C? OC2H5) 3 which results from the cleavage of the carbon carbon triple bond. The alkyne 2b however yields the vinylidene cluster Fe3(CO)10(m?32-C? C(H)OC2H5) 4 by 1,2 proton shift. The alkyne clusters Fe3(CO)10(m?32-C? C(H)OC2H5) 4 by 1,2 proton shift. The alkyne clusters Fe3(CO)10(m?32- H3 C? O? CH2? C?C? CH2? O? CH3) 6 and Fe3(CO)9(m?-η2-H3C? O? CH2? C?C? CH2? O? CH3) 7 are the isolated products obtained from 2c . Thermolysis of 7 results in the formation of the dinuclear butatrien complex Fe2(CO)6 (H2C? C? C? CH2) 8a . The analogous compound Fe2(CO)6[H(H3C)C ? C ? C ? C(CH3)H] 8b is the only product of 2d and 1 . The structures of 4, 5 , and 6 have been determined by crystal structure determinations.  相似文献   

6.
Homo- and heteroleptic aryloxides of the type MX4–x(OAr)x [M = TiIV, ZrIV; X = OPri, Cl; x = 1,2,3,4; OAr = OC6H4Pri-4(OAr1), OC6H3Me-2-Pri-5(OAr2), OC6H3Me-5-Pri-2(OAr3), OC6H2Me3-2,4,6(OAr4), OC6H3But2-2,4(OAr5), OC6H3But2-2,6(OAr6)] have been prepared either by alkoxo–aryloxo or chloro-aryloxo exchange reactions in benzene or tetrahydrofuran. All these new derivatives have been characterized by elemental analyses, spectroscopic (i.r., 1H-, 13C-n.m.r.) studies and molecular weight measurements. The FAB mass spectral studies of four representative derivatives Support a dimeric nature for [Ti(OC6H3Me-5-Pri-2)4], [TiCl2(OC6H3Me-5-Pri-2)2], and [Zr(OC6H3But2-2,4)4(thf)], whereas the derivative [ZrCl(OC6H3But2-2,4)3(thf)] is monomeric.  相似文献   

7.
In this article, water exchange reactions on [Be(L)(H2O)3]2+ (L?=?NH3? x (CH3) x , PH3? x (CH3) x , AsH3? x (CH3) x , OH2? x (CH3) x , SH2? x (CH3) x , SeH2? x (CH3) x , pyridine, 4-fluoropyridine, 4-bromopyridine, 4-chloropyridine, 4-hydroxypyridine, 4-thiolopyridine, 4-selenidopyridine, 4-nitrilopyridine, 1,4-diazine, 1,3,5-triazine, HCN, acetonitrile, and benzonitrile) are examined, utilizing the B3LYP//6-311?+?G** density functional for geometry optimizations, and B3LYP//6-311?+?G** both with and without the CPCM solvent model as well as MP2(full)//6-311?+?G** for subsequent single-point energy calculations. In all examined cases, the results prove that these complexes show associative interchange mechanisms for water exchange. With the exception of the NH x (CH3)3? x series of ligands, activation energy barriers vary little, making these ligands mostly spectator ligands. Geometrical parameters vary mainly with the ligand size.  相似文献   

8.
Organotin compounds R3Sn(CH2)n+2OC6H4C6H4Y (R3=Ph3, Ph2Bu; Y=H, CN; n=1-3) and RX2Sn(CH2)n+2OC6H4C6H4Y (R=Ph, Bu; Y=H, CN; X=Br, I; n=1-3) have been synthesised and characterised by 1H-, 13C-, 119Sn-NMR and Mössbauer spectroscopies. X-ray crystallography reveals tetrahedral geometries for Ph3Sn(CH2)4OC6H4C6H5 and Ph3Sn(CH2)3OC6H4C6H4CN, a six-coordinated, bromine-bridged dimeric structure for PhBr2Sn(CH2)3OC6H4C6H5 containing a mer-Br3C2OSn coordination sphere about tin and a five-coordinated monomeric structure for PhBr2Sn(CH2)3OC6H4C6H4CN. In all cases there is strong alignment of mesogenic groups in the solid-state but only PhBr2Sn(CH2)3OC6H4C6H4CN shows any indication of liquid-crystal behaviour. Wurtz polymerisation of RBr2Sn(CH2)5OC6H4C6H5 (R=Ph, Bu), both of which contain non-chelating ether functions, generated polystannanes (RR′Sn)n with Mn 2.3×105; Mw 3.0×105; Mw/Mn 1.30 and Mn 1.3×105; Mw 2.5×105; Mw/Mn 1.96, respectively, while no polymer was obtained from chelated PhBr2Sn(CH2)3OC6H4C6H5  相似文献   

9.
Polymerization of homologues of 1-(trimethylsilyl)-1-propyne [CH3C?CSi(CH3)3] was studied. CH3C?CSi(CH3)2(n-C6H13) ( I ) polymerized with 1 : 1 mixtures of TaCl5 and organometallic cocatalysts (e.g., Ph4Sn and Ph3Bi) to produce in good yields a polymer having a weight-average molecular weight (M w) over 1 × 106. CH3C?CSi(CH3)2 Ph ( II ) and CH3C?CSi(C2H5)3 ( III ) formed polymers having M w's of ~ 5 × 105 in moderate yields in the presence of TaCl5-based catalysts. In contrast, none of CH3C?CSi(CH3)2(i-C3H7), CH3C? CSi(CH3)2(t,-C4H9), C2H5C?CSi(CH3)3, and n,-C4H9C?CSi(CH3)3 polymerized, which is attributed to the steric effect of the monomers. Some other 1-silyl-1-propynes also failed to polymerize. The three new polymers formed from ( I )–( III ) had the structure \documentclass{article}\pagestyle{empty}\begin{document}$\rlap{--} [{\rm CCH}_{\rm 3} \hbox{=\hskip-2pt=} {\rm C(SiRR'R''}\rlap{--} ]_n$\end{document} according to IR and 13C-NMR spectra. They were white solids, soluble in low-polarity solvents (e.g., toluene and chloroform) and stable enough in air at room temperature.  相似文献   

10.
Symmetrical and asymmetrical triphenylene discotic liquid crystals with two kinds of different peripheral chains, sym-TP(OC11H23)3(O2CR)3 and asym-TP(OC11H23)3(O2CR)3, (R=CH2OC2H5, CH2OC3H7, CH2OC4H9, CH2OC5H11, C3H7, C4H9, C5H11, C6H13, C7H15) were synthesized. Their thermotropic liquid crystalline properties were studied by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The results showed that the asymmetrical compounds had higher melting and clearing points than that of their corresponding symmetrical compounds. For the same series of compounds, TP(OC11H23)3(O2CR)3, their melting points decrease and clearing points increase gradually with the lengthening of ester chains. Most of the β-oxygen containing esters of triphenylene derivatives, TP (OC11H23)3(O2CR)3, (R=CH2OC2H5, CH2OC3H7, CH2OC4H9, CH2OC5H11), symmetrically or asymmetrically attached on triphenylene cores, have higher melting and clearing points than those of triphenylene derivatives, TP(OC11H23)3(O2CR)3, (R=C4H9, C5H11, C6H13, C7H15), with the same length of peripheral chains. The triphenylene derivatives with longer peripheral chains have shown mesophase at room temperature. __________ Translated from Chemical Research and Application, 2007, 19(10) (in Chinese)  相似文献   

11.
The reaction of triphenylbismuth, hydrogen peroxide, and phenol (molar ratio 1 : 1 : 2) in ether was used to synthesize triphenylbismuth diaroxides Ph3Bi(OAr)2 [Ar = C6H3(NO2)2-2,4, C6H2(NO2)3-2,4,6, C6H3Cl2-2,6, C6H2Cl3-2,4,6, C6H3Br2-2,4, C6H2Br3-2,4,6, C6H2Br2-2,4,Me-6, C6H2Br2-2,6, NO2-4]. At an equimolar reagent ratio, bridged bismuth compounds (Ph3BiOAr)2O are formed. The crystal structure of bis-(2,4-dinitrophenoxy)triphenylbismuth Ph3Bi[OC6H3(NO2)2-2,4]2 was studied by X-ray diffraction to show that the bismuth atom has a distorted trigonal bipyramidal coordination and the 2,4-dinitrophenoxyl ligands are axial. The CBiC and OBiO angles are 109.6(5)°, 122.3(5)°, 128.1(5)°, and 175.6(3)°. The Bi-O1,6 and Bi-C bond lengths are 2.256(10), 2.242(9) and 2.18(1), 2.18(1), 2.19(1) Å, respectively.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 927–929.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Tsiplukhina, Molokov, Fukin.  相似文献   

12.
Extraction of Ln(III), Sc(III), Ga(III), and Re(VII) ions by solutions of phosphorylated monopodands having [ortho-(diphenylphosphinylmethyl)-para-methyl]phenyl terminal groups, 2-Ph2P(O)CH2(4-Me)C6H3(OCH2CH2) n OC6H3(Me-4)CH2P(O)Ph2-2 (n = 1–5), in organic solvents has been studied. The stoichiometries of extractable complexes were determined. The effect of the aqueous phase, organic solvent, and phosphorylated podand structure on the efficacy of metal-ion recovery into organic phase has been considered.  相似文献   

13.
[VOCl(OC6H3(NO2)2-2,4)2] (1) has been synthesized by the reaction of VOCl3 with bimolar amounts of Me3SiOC6H3(NO2)2-2,4 in toluene and characterized by elemental analyses, molar conductance, infrared (IR), 1H and 13C NMR and mass spectral, and thermal studies. Molecular modeling dynamics of the complex suggests tetrahedral geometry around vanadium. The reaction of 1 with sodium alkoxides, NaOR (OR?=?OMe (methoxy); OEt (ethoxy), OBun(n-butoxy); OPri (isopropoxy); and OAmi(isoamyloxy)) afforded mixed alkoxo–phenoxo complexes, [VO(OR)(OC6H3(NO2)2-2,4)2] authenticated by physicochemical and IR spectral studies. The antifungal activities of the ligand and complexes against three fungi, namely Aspergillus niger, Byssachlamys fulva, and Mucor circinelloides have been assayed by the minimum inhibitory concentration method. The complexes have improved antifungal activity compared to free ligand.  相似文献   

14.
A series of complexes of formula, [(Ph3P)2PtCH2=CHSi (CH3)n(OC2H5)3---n] (n = 0,1,2,3), has been prepared and characterized. The all carbon compound, [(Ph3P)2PtCH2=CHC (CH3)3], has also been prepared and found to decompose in solution much more readily than its silicon analogue.  相似文献   

15.
Abstract

A homologous series of di(4-alkyloxybenzoates) of 4,4′-dimercaptobiphenyl: CH3(CH2) n-1O?C6H4?COS?C6H4?C6H4?SOC?C6H4?O(CH2) n-1CH3,n=1–7, has been synthesized and the thermotropic liquid-crystalline behaviour investigated. All compounds exhibit enantiotropic mesomorphism over a remarkable temperature range. While the mesophase thermal stability is moderately higher than that found for the corresponding oxygenated analogues, the smectic stability is definitely lower. In fact, all the compounds are nematic but smectic mesomorphism (SC) is observed for n = 7. Compounds with n = 6 or 7 exhibit enantiotropic highly ordered smectic (or disordered crystal) phases, probably SG in type.  相似文献   

16.
Six new complexes, Mn(CO)( 5-C5H5){Ph2P(S)(CH2) n P(S)Ph2}] (1a3a) [(1a), n=1; (2a), n=2; (3a), n=3] and [Mn2(CO)4( 5-C5H5)2(cis--Ph2P(S)(CH2) n P(S)Ph2)] (1b–3b) [(1b), n=1; (2b), n=2; (3b), n=3] have been synthesized by the photochemical reaction of [( 5-C5H5)Mn(CO)3] with Ph2P(S)(CH2) n P(S)Ph2 [n=1, dppm(S)2; 2, dppe(S)2; 3, dppp(S)2]. The complexes have been characterized by elemental analysis, mass spectroscopy, f.t.-i.r. and 31P–[1H]-n.m.r. spectroscopy. The spectroscopic studies reveal that coordination of the ligand iscis-chelate bidentate in [Mn(CO)( 5-C5H5){Ph2P(S)(CH2) n P(S)Ph2}] (1a3a) and cis-bridging bidentate between two metals in [Mn2(CO)4( 5-C5H5)2(cis--Ph2P(S)(CH2) n P(S)Ph2)] (1b–3b).  相似文献   

17.
Thermal behaviour of newly synthesized niobium(V) aryloxides of composition [NbCl5−n (OC6H4CH(CH3)2-4) n ] (where n = 1 → 5) synthesized by the reactions of niobium pentachloride with 4-isopropylphenol in predetermined molar ratios in carbon tetrachloride has been studied by thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The results showed that thermal decomposition of complex of composition [NbCl4(OC6H4CH(CH3)2-4)] resulted in the formation of NbOCl3 as the ultimate decompositional product while all other complexes yielded Nb2O5 as the final product of thermal decomposition. From the mathematical analysis of TG data, the kinetic and thermodynamic parameters viz. energy of activation, frequency factor, entropy of activation, etc. have been evaluated using Coats–Redfern equation.  相似文献   

18.
Connecting two discotic mesogens via a spacer not only stabilizes the columnar mesophase but also leads to the formation of glass columnar phase, and therefore improves the physical properties of discotic liquid crystals as organic semiconductor. Here, we report the synthesis of eight diacetylene-bridged triphenylene discotic liquid crystal dimers, [C18H6(OCnH2n+1)4(OMe)O2C-C8H16-C≡≡ C-]2, 3(n), (n = 4-8), [C18H6(OC6H13)5O2C-C8H16-C≡≡ C-]2, 6 and [C18H6(OC6H13)5O-(CH2)m-C≡≡ C-]2, 8(m), (m = 1, 3) by Eglinto...  相似文献   

19.
通过2-甲酰基吡啶与胺缩合制得Schiff碱,经NaBH4还原得到四个N-(2-吡啶甲基)芳胺(芳基=苯基,邻甲氧基苯基,对甲苯基及2-吡啶基),得到的芳胺及N-(2-吡啶乙基)甲胺与三甲基镓反应生成相应的N-(2-吡啶基)伯胺·二甲基合镓(Ⅲ)配合物。用元素分析、红外光谱、质子核磁共振、质谱等手段对配合物进行了结构鉴定和表征。  相似文献   

20.
Guoxiong Hua 《Tetrahedron》2009,65(31):6074-6987
2,4-Bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide (Woollins’ reagent, WR) reacts with cyanamides (1a-h) in refluxing toluene to afford a series of novel selenazadiphospholaminediselenides (RR′NCN(PhP(Se)SeP(Se)Ph, R=C6H5(CH2)1-3, 4-n-C10H21C6H4 and 4-BrC6H4CH2; R′=H, CH3, C2H5 and C(O)OC2H52a-g). Post-treatment of the reaction mixture with water led to the formation of carbamidoyl(phenyl)phosphinodiselenoic acids (RR′NC(NH2)P(SeH)2Ph, R=C6H5(CH2)2-3, 4-n-C10H21C6H4 and 4-BrC6H4CH2; R′=H and CH3, 3b, 3c, 3e and 3f) and selenoureas (RR′NC(Se)NH2, R=C6H5(CH)1-2; R′=CH3 and OC(O)C2H5, 4f and 4h) in moderate to excellent yields. All new compounds are characterised spectroscopically and five X-ray crystal structures are reported.  相似文献   

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