共查询到20条相似文献,搜索用时 78 毫秒
1.
Sagisaka M Iwama S Hasegawa S Yoshizawa A Mohamed A Cummings S Rogers SE Heenan RK Eastoe J 《Langmuir : the ACS journal of surfaces and colloids》2011,27(10):5772-5780
The fluorinated double-tailed glutarate anionic surfactant, sodium 1,5-bis[(1H,1H,2H,2H-perfluorodecyl)oxy]-1,5-dioxopentane-2-sulfonate (8FG(EO)(2)), was found to stabilize water-in-supercritical CO(2) microemulsions with high water-to-surfactant molar ratios (W(0)). Studies were carried out here to obtain detailed information on the phase stability and nanostructure of the microemulsions by using a high-pressure UV-vis dye probe and small-angle neutron scattering (SANS) measurements. The UV-vis spectra, with methyl orange as a reporter dye, indicated a maximum attainable W(0) of 60 at 45 and 75 °C, and SANS profiles indicated regular droplet swelling with a linear relationship between the water core nanodroplet radius and W(0). This represents the highest water solubilization reported to date for any water-in-CO(2) microemulsion. Further analysis of the SANS data indicated critical packing parameters for 8FG(EO)(2) at the microemulsion interface >1.34, representing approximately 1.1 times the value for common aerosol-OT in water-in-heptane microemulsions under equivalent conditions. 相似文献
2.
Sagisaka M Fujii T Ozaki Y Yoda S Takebayashi Y Kondo Y Yoshino N Sakai H Abe M Otake K 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2560-2566
We have examined the interfacial properties of several fluorinated surfactants in a water/CO2 mixture with a pendant drop tensiometer and revealed the relationships between the interfacial properties, the surfactant structure, and the microemulsifying power. We employed the following Aerosol-OT analogue surfactants that have two fluorinated tails: bis(1H,1H,5H-octafluoropentyl)-2-sulfosuccinate (di-HCF4), sodium bis(1H,1H,9H-hexadecafluorononyl)-2-sulfosuccinate (di-HCF8), sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO)2), and sodium bis((1H,1H,2H,2H-heptadecafluorodecyl)-oxyethylene)-2-sulfosuccinate (8FS(EO)4). To discuss the effect of the fluorocarbon/hydrocarbon ratio in single surfactant molecules, water/CO2 interfacial tension (IFT) of a hybrid surfactant with one fluorocarbon and one hydrocarbon tail, that of a surfactant with a single fluorinated tail, and that of a hydrocarbon surfactant, Aerosol-OT (AOT), were examined. The hybrid surfactant employed was sodium 1-oxo-1-[4-(tridecafluorohexyl)phenyl]-2-hexanesulfonate (FC6-HC4), and the single-tailed surfactant was perfluoropolyether ammonium carboxylate (PFPECOONH4, CF3CF2(CF2OCF(CF3))4COONH4). All of the fluorinated AOT analogue surfactants exhibited an excellent level of activity at the water/CO2 interface compared with other fluorinated surfactants and AOT. With a larger hydrocarbon chain number in the CO2-philic tails (i.e., from 0 to 2), the IFT of the AOT analogue surfactants was increased. The area occupied by one surfactant molecule at the water/CO2 interface, A, and the critical microemulsion concentration, cmicroc, were determined and used to examine the water-to-surfactant molar ratio within a reversed micelle, W0c, of the surfactants. The surfactants that form W/scCO2 microemulsions with a large W0c were found to lower the interfacial tension efficiently irrespective of increases in temperature. To achieve the most desirable W0C, the surfactant needs not only a high CO2-philicity of the tails but also a high Krafft point, properties which induce a low hydrophilic/CO2-philic balance. 相似文献
3.
Sagisaka M Koike D Mashimo Y Yoda S Takebayashi Y Furuya T Yoshizawa A Sakai H Abe M Otake K 《Langmuir : the ACS journal of surfaces and colloids》2008,24(18):10116-10122
Phase behavior was investigated for water/supercritical CO 2 (W/scCO2) microemulsions stabilized with sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO) 2) mixed with various guest surfactants. Only for the mixtures with fluorocarbon-hydrocarbon hybrid anionic surfactants (FC6-HC n), the maximum water-to-surfactant molar ratio (W0(c)) was larger than that estimated from linear interpolation of the W0(c) values for pure 8FS(EO) 2 and pure guest surfactant. Fourier transform infrared (FT-IR) measurement for the microemulsion revealed that the mixing of 8FS(EO) 2 with FC6-HC n can prevent a phase transition from the microemulsion to the liquid crystal even in the presence of excess water. It was also found from the measurement of water/scCO 2 interfacial tension that the area occupied per surfactant molecule was markedly increased by the mixing with FC6-HC n. The loose molecular packing, probably due to a microsegregation of 8FS(EO) 2 and FC6-HC n, is consistent with the enhanced stability of the microemulsion upon surfactant mixing. 相似文献
4.
Zhang R Liu J He J Han B Wu W Jiang T Liu Z Du J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2167-2172
Nanometer-sized gold particles are synthesized by the reduction of HAuCl(4) with KBH(4) in the CO(2)-induced microemulsion of (EO)(27)(PO)(61)(EO)(27) (P104; EO=ethylene oxide, PO=propylene oxide)/p-xylene/CO(2)/H(2)O. The recovery of gold particles from the microemulsion can be easily accomplished by the venting of CO(2), while the surfactant remains in the organic phase. The effect of the molar ratio of the reductant to HAuCl(4), the concentration of the reactants, and the molar ratio of water to EO segments (W(0)) in the reverse micelles on the size of the gold particles is studied. The hydrolysis of benzoyl chloride (BzCl) and p-nitrophenyl chloroformate (NPhCl) has also been carried out in the microemulsion. The results show that the observed rate constants k(obs) of both substrates increase significantly with W(0), and that W(0) has a larger influence on the hydrolysis of BzCl. The different extents of the influence of W(0) on the two reactions can be ascribed to the different reaction mechanisms and the expected changes in nucleophilicity and polarity of water in the reverse micelles. 相似文献
5.
Roberts JA Franz JA van der Eide EF Walter ED Petersen JL DuBois DL Bullock RM 《Journal of the American Chemical Society》2011,133(37):14593-14603
A series consisting of a tungsten anion, radical, and cation, supported by the N-heterocyclic carbene 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) and spanning formal oxidation states W(0), W(I), and W(II), has been synthesized, isolated, and characterized. Reaction of the hydride CpW(CO)(2)(IMes)H with KH and 18-crown-6 gives the tungsten anion [CpW(CO)(2)(IMes)](-)[K(18-crown-6)](+). Electrochemical oxidation of [CpW(CO)(2)(IMes)](-) in MeCN (0.2 M (n)Bu(4)N(+)PF(6)(-)) is fully reversible (E(1/2) = -1.65 V vs Cp(2)Fe(+?/0)) at all scan rates, indicating that CpW(CO)(2)(IMes)(?) is a persistent radical. Hydride transfer from CpW(CO)(2)(IMes)H to Ph(3)C(+)PF(6)(-) in MeCN affords [cis-CpW(CO)(2)(IMes)(MeCN)](+)PF(6)(-). Comproportionation of [CpW(CO)(2)(IMes)](-) with [CpW(CO)(2)(IMes)(MeCN)](+) gives the 17-electron tungsten radical CpW(CO)(2)(IMes)(?). This complex shows paramagnetically shifted resonances in the (1)H NMR spectrum and has been characterized by IR spectroscopy, low-temperature EPR spectroscopy, and X-ray diffraction. CpW(CO)(2)(IMes)(?) is stable with respect to disproportionation and dimerization. NMR studies of degenerate electron transfer between CpW(CO)(2)(IMes)(?) and [CpW(CO)(2)(IMes)](-) are reported. DFT calculations were carried out on CpW(CO)(2)(IMes)H, as well as on related complexes bearing NHC ligands with N,N' substituents Me (CpW(CO)(2)(IMe)H) or H (CpW(CO)(2)(IH)H) to compare to the experimentally studied IMes complexes with mesityl substituents. These calculations reveal that W-H homolytic bond dissociation energies (BDEs) decrease with increasing steric bulk of the NHC ligand, from 67 to 64 to 63 kcal mol(-1) for CpW(CO)(2)(IH)H, CpW(CO)(2)(IMe)H, and CpW(CO)(2)(IMes)H, respectively. The calculated spin density at W for CpW(CO)(2)(IMes)(?) is 0.63. The W radicals CpW(CO)(2)(IMe)(?) and CpW(CO)(2)(IH)(?) are calculated to form weak W-W bonds. The weakly bonded complexes [CpW(CO)(2)(IMe)](2) and [CpW(CO)(2)(IH)](2) are predicted to have W-W BDEs of 6 and 18 kcal mol(-1), respectively, and to dissociate readily to the W-centered radicals CpW(CO)(2)(IMe)(?) and CpW(CO)(2)(IH)(?). 相似文献
6.
F. Comelles J. Sánchez‐Leal J. J. González 《Journal of Dispersion Science and Technology》2013,34(8):1218-1222
Soy oil microemulsions has been optimized for systems made of phosphated oleyl ether 3EO as surfactant, oleic acid, diethyleneglycol monoethyl ether, and water. The soy oil solubilization has been estimated as a function of different ratios between surfactant/oleic acid (5/95, 10/90, 15/85, and 20/80) and water/glycol (4/1, 2/1, 1/1, 1/2, and 1/4). The maximum simultaneous solubilization of soy oil and hydrophilic phase (water plus glycol) in ratios 3/1, 1/1, and 1/3 (besides the 1/0 and 0/1) was considered. In order to display the widest microemulsion area, the better ratios surfactant/oleic acid were 10/90, 15/85, and 20/80 when water and glycol ratios were 1/2 and 1/4. For these systems, the transition between W/O, bicontinuous and O/W microemulsions were followed through electrical conductivity changes. 相似文献
7.
The reaction of CpMoMn(mu-S(2))(CO)(5), 1, with 1,4-benzoquinone in the presence of irradiation with visible light yielded the quinonedithiolato complex CpMoMn(CO)(5)(mu-S(2)C(6)H(2)O(2)), 2. The new complex CpMoMn(CO)(5)(mu-S(2)C(6)Cl(2)O(2)) (4) was synthesized similarly from 1 and 2,3-dichloro-1,4-benzoquinone. Compounds 2 and 4 were reduced with hydrogen to yield the hydroquinone complexes CpMoMn(CO)(5)[mu-S(2)C(6)H(2)(OH)(2)], 3, and CpMoMn(CO)(5)[mu-S(2)C(6)Cl(2)(OH)(2)], 5. UV-vis irradiation of solutions of Fe(2)(CO)(6)(mu-S(2)) and 1,4-benzoquinone yielded the hydroquinone complex Fe(2)(CO)(6)[mu-S(2)C(6)H(2)(OH)(2)], 6. Compound 6 was oxidized to the quinone complex Fe(2)(CO)(6)(mu-S(2)C(6)H(2)O(2)), 7, by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Substitution of the CO ligands on 6 by PPh(3) yielded the derivatives Fe(2)(CO)(5)(PPh(3))[mu-S(2)C(6)H(2)(OH)(2)], 8, and Fe(2)(CO)(4)(PPh(3))(2)[mu-S(2)C(6)H(2)(OH)(2)], 9. The electrochemical properties of 3, 5, 6, 8, and 9 were measured by cyclic voltammetry. The molecular structure of each of the new compounds 2-9 was established by single-crystal X-ray diffraction analyses. 相似文献
8.
da Rocha SR Psathas PA Klein E Johnston KP 《Journal of colloid and interface science》2001,239(1):241-253
Concentrated CO(2)-in-water (C/W) emulsions are reported for amphiphiles containing alkylene oxide-, siloxane-, and fluorocarbon-based tails as a function of temperature and salinity. Poly(ethylene oxide)-b-poly(butylene oxide) (EO(15)-b-BO(12)) can emulsify up to 70% CO(2) with droplet sizes from 2 to 4 &mgr;m in diameter, as determined by video-enhanced microscopy. This emulsion is stable over 48 h against both flocculation and coalescence. In contrast, it is extremely difficult to form concentrated water-in-CO(2) (W/C) emulsions with surfactants containing alkylene oxide moieties due to limited solvation of such tails by CO(2). In several cases, C/W emulsions are formed even when the surfactant prefers CO(2). This violation of Bancroft's rule may be attributed in part to the low viscosity of the compressed CO(2), which governs several mass and momentum transport mechanisms relevant to emulsion formation and stabilization. For the first time, W/C microemulsions are observed in a system with a nonionic amphiphile, namely F(CF(2)CF(2))(3-8)CH(2)CH(2)O(CH(2)CH(2)O)(10-15)H. For the same system, the emulsion morphology changes from C/W to W/C as the temperature increases. The electrical conductivity of C/W emulsions is predicted successfully as a function of the dispersed phase volume fraction of CO(2) with Maxwell's theory for inhomogeneous systems. Copyright 2001 Academic Press. 相似文献
9.
Glöckner A Bannenberg T Büschel S Daniliuc CG Jones PG Tamm M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(22):6118-6128
The transmetalation reaction between [(η(7) -C(7) H(7) )ZrCl(tmeda)] (1; tmeda=N,N,N',N'-tetramethylethylenediamine) and various phospholide anions leads to a new class of mixed sandwich complexes: [(η(7)-C(7)H(7))Zr(η(5)-C(4)PMe(4))] (2), [(η(7)-C(7)H(7))Zr(η(5)-C(4)PH(2)Me(2))] (3) and [(η(7)-C(7)H(7))Zr(η(5)-C(4)PPhHMe(2))] (4). The presence of Lewis basic phosphorus atoms and Lewis acidic zirconium atoms allows ambiphilic behaviour to be observed, and X-ray diffraction analysis reveals dimeric arrangements for 2 and 3 with long intermolecular Zr-P bonds, whereas 4 remains monomeric in the solid state. DFT calculations indicate that the metal-phosphorus interaction is weak, and accordingly, complexes 2-4 act as monodentate ligands upon reaction with [W(CO)(5)(thf)]. The resulting complexes [W(CO)(5)(L)] 5-7 (L=2-4) were studied by IR spectroscopy and compared with the [W(CO)(5) ] complex 9, containing the phosphane-functionalised trozircene [(η(7)-C(7)H(7))Zr(η(5)-C(5)H(4)PPh(2))] (8). They all show a close resemblance to simple phosphanes, such as PMe(3) , although molecular orbital analysis of 2 reveals that the free electron pair in the phosphatrozircenes is not the HOMO. Four equivalents of 2 can replace 1,4-cyclooctadiene (COD) in [Ni(cod)(2)] to form the homoleptic, distorted tetrahedral complex [Ni{2}(4)] (10). 相似文献
10.
Wagner M Dorogov K Schürmann M Jurkschat K 《Dalton transactions (Cambridge, England : 2003)》2011,40(35):8839-8848
The synthesis of the intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)Sn(X)W(CO)(5) (1, X = Cl; 2, X = F; 3, X = PPh(2)) and of 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)Sn[W(CO)(5)]PPh(2)[W(CO)(5)], 4, are reported. UV-irradiation of compound 4 in tetrahydrofurane serendipitously gave the bis(organostannylene) tungsten tetracarbonyl complex cyclo-O(2)W[OSn(R)](2)W(CO)(4) (R = 4-tBu-2,6-[P(O)(OiPr)(2)](2)C(6)H(2)), 5, that contains an unprecedented W(0)-Sn-O-W(vi) bond sequence. The compounds 1-5 were characterized by means of single crystal X-ray diffraction analysis, (1)H, (13)C, (19)F, (31)P, (119)Sn NMR, and IR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and elemental analysis. Compound 4 features a hindered rotation about the Sn-P bond. 相似文献
11.
Ghadwal RS Azhakar R Pröpper K Holstein JJ Dittrich B Roesky HW 《Inorganic chemistry》2011,50(17):8502-8508
Reactions of N-heterocyclic carbene stabilized dichlorosilylene IPr·SiCl(2) (1) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with (η(5)-C(5)H(5))V(CO)(4), (η(5)-C(5)H(5))Co(CO)(2), and Fe(2)(CO)(9) afford dichlorosilylene complexes IPr·SiCl(2)·V(CO)(3)(η(5)-C(5)H(5)) (2), IPr·SiCl(2)·Co(CO)(η(5)-C(5)H(5)) (3), and IPr·SiCl(2)·Fe(CO)(4) (4), respectively. Complexes 2-4 are stable under an inert atmosphere, are soluble in common organic solvents, and have been characterized by elemental analysis and multinuclear ((1)H, (13)C, and (29)Si) NMR spectroscopy. Molecular structures of 2-4 have been determined by single crystal X-ray crystallographic studies and refined with nonspherical scattering factors. 相似文献
12.
N M Deschamps J H Kaldis P E Lock J F Britten M J McGlinchey 《The Journal of organic chemistry》2001,66(25):8585-8591
Treatment of 1-[axial]-(trimethylsilylethynyl)cyclohexan-1-ol with dicobalt octacarbonyl results in a conformational ring flip such that the bulky dicobalt-alkyne cluster moiety now occupies the favored equatorial site. However, when a 4-tert-butyl substituent is present, the coordinated alkynyl group retains its original axial or equatorial position. Complexation of trans-[diaxial]-1,4-bis(triphenylsilylethynyl)cyclohexane-1,4-diol brings about a chair-to-chair conformational inversion such that both cluster fragments now occupy equatorial sites. In contrast, cis-1,4-bis(triphenylsilylethynyl)cyclohexane-1,4-diol reacts with Co(2)(CO)(8) to yield the twist-boat conformer in which the two axial hydroxy substituents exhibit intra-molecular hydrogen bonding. Likewise, the corresponding reaction of cis-1,4-bis(trimethylsilylethynyl)cyclohexane-1,4-diol with Co(2)(CO)(8) leads to a twist-boat, but in this case, the molecules are linked through inter-molecular hydrogen bonds. Eight of these cobalt clusters have been characterized by X-ray crystallography, and the potential use of twist-boats in synthesis is discussed. 相似文献
13.
Liu T Chen S O'Hagan MJ Rakowski DuBois M Bullock RM DuBois DL 《Journal of the American Chemical Society》2012,134(14):6257-6272
The iron complexes CpFe(P(Ph)(2)N(Bn)(2))Cl (1-Cl), CpFe(P(Ph)(2)N(Ph)(2))Cl (2-Cl), and CpFe(P(Ph)(2)C(5))Cl (3-Cl)(where P(Ph)(2)N(Bn)(2) is 1,5-dibenzyl-1,5-diaza-3,7-diphenyl-3,7-diphosphacyclooctane, P(Ph)(2)N(Ph)(2) is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane, and P(Ph)(2)C(5) is 1,4-diphenyl-1,4-diphosphacycloheptane) have been synthesized and characterized by NMR spectroscopy, electrochemical studies, and X-ray diffraction. These chloride derivatives are readily converted to the corresponding hydride complexes [CpFe(P(Ph)(2)N(Bn)(2))H (1-H), CpFe(P(Ph)(2)N(Ph)(2))H (2-H), CpFe(P(Ph)(2)C(5))H (3-H)] and H(2) complexes [CpFe(P(Ph)(2)N(Bn)(2))(H(2))]BAr(F)(4), [1-H(2)]BAr(F)(4), (where BAr(F)(4) is B[(3,5-(CF(3))(2)C(6)H(3))(4)](-)), [CpFe(P(Ph)(2)N(Ph)(2))(H(2))]BAr(F)(4), [2-H(2)]BAr(F)(4), and [CpFe(P(Ph)(2)C(5))(H(2))]BAr(F)(4), [3-H(2)]BAr(F)(4), as well as [CpFe(P(Ph)(2)N(Bn)(2))(CO)]BAr(F)(4), [1-CO]Cl. Structural studies are reported for [1-H(2)]BAr(F)(4), 1-H, 2-H, and [1-CO]Cl. The conformations adopted by the chelate rings of the P(Ph)(2)N(Bn)(2) ligand in the different complexes are determined by attractive or repulsive interactions between the sixth ligand of these pseudo-octahedral complexes and the pendant N atom of the ring adjacent to the sixth ligand. An example of an attractive interaction is the observation that the distance between the N atom of the pendant amine and the C atom of the coordinated CO ligand for [1-CO]BAr(F)(4) is 2.848 ?, considerably shorter than the sum of the van der Waals radii of N and C atoms. Studies of H/D exchange by the complexes [1-H(2)](+), [2-H(2)](+), and [3-H(2)](+) carried out using H(2) and D(2) indicate that the relatively rapid H/D exchange observed for [1-H(2)](+) and [2-H(2)](+) compared to [3-H(2)](+) is consistent with intramolecular heterolytic cleavage of H(2) mediated by the pendant amine. Computational studies indicate a low barrier for heterolytic cleavage of H(2). These mononuclear Fe(II) dihydrogen complexes containing pendant amines in the ligands mimic crucial features of the distal Fe site of the active site of the [FeFe]-hydrogenase required for H-H bond formation and cleavage. 相似文献
14.
Reactions between 2,6-diformyl-4-methylphenol (DFMF) and tris(hydroxymethyl) aminomethane (THMAM = H(3)L2) in the presence of copper(II) salts, CuX(2) (X = CH(3)CO(2)(-), BF(4)(-), ClO(4)(-), Cl(-), NO(3)(-)) and Ni(CH(3)CO(2))(2) or Ni(ClO(4))(2)/NaC(6)H(5)CO(2), sodium azide (NaN(3)), and triethylamine (TEA), in one pot self-assemble giving a coordination polymer consisting of repeating pentanuclear copper(II) clusters {[Cu(2)(H(5)L(2-))(μ-N(3))](2)[Cu(N(3))(4)]·2CH(3)OH}(n) (1) and hexanuclear Ni(II) complexes [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(CH(3)CO(2))(2)]·6C(3)H(7)NO·C(2)H(5)OH (2) and [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(C(6)H(5)CO(2))(2)]·3C(3)H(7)NO·3H(2)O·CH(3)OH (3). In 1, H(5)L(2-) and in 2 and 3 H(3)L1(-) and HL2(2-) represent doubly deprotonated, singly deprotonated, and doubly deprotonated Schiff-base ligands H(7)L and H(4)L1 and a tripodal ligand H(3)L2, respectively. 1 has a novel double-stranded ladder-like structure in which [Cu(N(3))(4)](2-) anions link single chains comprised of dinuclear cationic subunits [Cu(2)(H(5)L(2-))(μ-N(3))](+), forming a 3D structure of interconnected ladders through H bonding. Nickel(II) clusters 2 and 3 have very similar neutral hexanuclear cores in which six nickel(II) ions are bonded to two H(4)L1, two H(3)L2, four μ-azido, and two μ-CH(3)CO(2)(-)/μ-C(6)H(5)CO(2)(-) ligands. In each structure two terminal dinickel (Ni(2)) units are connected to the central dinickel unit through four doubly bridging end-on (EO) μ-azido and four triply bridging μ(3)-methoxy bridges organizing into hexanuclear units. In each terminal dinuclear unit two nickel centers are bridged through one μ-phenolate oxygen from H(3)L1(-), one μ(3)-methoxy oxygen from HL2(2-), and one μ-CH(3)CO(2)(-) (2)/μ-C(6)H(5)CO(2)(-) (3) ion. Bulk magnetization measurements on 1 show moderately strong antiferromagnetic coupling within the [Cu(2)] building block (J(1) = -113.5 cm(-1)). Bulk magnetization measurements on 2 and 3 demonstrate that the magnetic interactions are completely dominated by ferromagnetic coupling occurring between Ni(II) ions for all bridges with coupling constants (J(1), J(2), and J(3)) ranging from 2.10 to 14.56 cm(-1) (in the ? = -J(1)(?(1)?(2)) - J(1)(?(2)?(3)) - J(2)(?(3)?(4)) - J(1)(?(4)?(5)) - J(1)(?(5)?(6)) - J(2)(?(1)?(6)) - J(3)(?(2)?(6)) - J(3)(?(2)?(5)) - J(3)(?(3)?(5)) convention). 相似文献
15.
Chen CH Chen CS Dai HF Yeh WY 《Dalton transactions (Cambridge, England : 2003)》2012,41(10):3030-3037
Following the method of Prato et al., reaction of C(60), N-methylglycine and o-(diphenylphosphino)benzaldehyde affords PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) in moderate yield. Compound 1 reacts with W(CO)(4)(NCMe)(2) to produce W(CO)(4)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), through coordination of the phosphine group and one 6 : 6-ring junction of fullerene. Reaction of 1 and Os(3)(CO)(11)(NCMe) affords Os(3)(CO)(11)(PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (3), which undergoes a cluster fragmentation reaction in refluxing toluene to produce Os(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (4). Thermal reaction of 1 and Os(3)(CO)(12) affords 3 and 4. On the other hand, reaction of 1 and Ru(3)(CO)(12) yields only the mononuclear complex Ru(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (5). The structures of 1-3 and 5 were determined by an X-ray diffraction study. 相似文献
16.
[{mu-(Pyridazine-N(1):N(2))}Fe(2)(mu-CO)(CO)(6)](1) reacts with aryllithium reagents, ArLi (Ar = C(6)H(5), m-CH(3)C(6)H(4)) followed by treatment with Me(3)SiCl to give the novel pyridazine-coordinated diiron bridging siloxycarbene complexes [(C(4)H(4)N(2))Fe(2){mu-C(OSiMe(3))Ar}(CO)(6)](2, Ar = C(6)H(5); 3, Ar =m-CH(3)C(6)H(4)). Complex 2 reacts with HBF(4).Et(2)O at low temperature to yield a cationic bridging carbyne complex [(C(4)H(4)N(2))Fe(2)(mu-CC(6)H(5))(CO)(6)]BF(4)(4). Cationic 4 reacts with NaBH(4) in THF at low temperature to afford the diiron bridging arylcarbene complex [(C(4)H(4)N(2))Fe(2){mu-C(H)C(6)H(5)}(CO)(6)](5). Unexpectedly, the reaction of 4 with NaSCH(3) under similar conditions gave the bridging arylcarbene complex 5 and a carbonyl-coordinated diiron bridging carbene complex [Fe(2){mu-C(SCH(3))C(6)H(5)}(CO)(7)](6), while the reaction of NaSC(6)H(4)CH(3)-p with 4 affords the expected bridging arylthiocarbene complex [(C(4)H(4)N(2))Fe(2){mu-C(SC(6)H(4)CH(3)-p)C(6)H(5)}(CO)(6)](7), which can be converted into a novel diiron bridging carbyne complex with a thiolato-bridged ligand, [Fe(2)(mu-CC(6)H(5))(mu-SC(6)H(4)CH(3)-p)(CO)(6)](8). Cationic can also react with the carbonylmetal anionic compound Na(2)[Fe(CO)(4)] to yield complex 5, while the reactions of 4 with carbonylmetal anionic compounds Na[M(CO)(5)(CN)](M = Cr, Mo, W) produce the diiron bridging aryl(pentacarbonylcyanometal)carbene complexes [(C(4)H(4)N(2))Fe(2)-{mu-C(C(6)H(5))NCM(CO)(5)}(CO)(6)](9, M = Cr; 10, M = Mo; 11, M = W). The structures of complexes 2, 5, 6, 8, and 9 have been established by X-ray diffraction studies. 相似文献
17.
Grenier CR George SJ Joncheray TJ Meijer EW Reynolds JR 《Journal of the American Chemical Society》2007,129(35):10694-10699
We report an efficient synthesis of chiral (2S)-ethylhexanol for functionalizing and solubilizing conjugated polymers. The alpha-substituted chiral ethylhexyl side chains were obtained through a powerful and flexible asymmetric synthesis using pseudoephedrine as a chiral auxiliary. The dependence of the properties of conjugated polymers on molecular structure is investigated by circular dichroism, fluorescence, and absorption spectroscopy on two new chiral conjugated polymers, poly(3,3-bis((S)-2-ethylhexyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine) (PProDOT((2S)-ethylhexyl)(2)) and poly(3,3-bis((S)-2-methylbutyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine) (PProDOT((2S)-methylbutyl)(2)). The properties of PProDOT((2S)-ethylhexyl)(2)) differ significantly from those of its methylbutyl analog as investigated by chiral aggregation providing insight into the role of interchain interactions in these subsecond switching electrochromic polymers. 相似文献
18.
Phase behavior and microstructures of nonionic fluorocarbon surfactant in aqueous systems 总被引:1,自引:0,他引:1
Shrestha RG Shrestha LK Sharma SC Aramaki K 《The journal of physical chemistry. B》2008,112(34):10520-10527
The phase behavior and self-assembled structures of perfluoroalkyl sulfonamide ethoxylate, C8F17SO2N(C3H7)(CH2CH2O)20H (abbreviated as C8F 17EO20), a nonionic fluorocarbon surfactant in an aqueous system, has been investigated by the small-angle X-ray scattering (SAXS) technique. The C8F17EO20 forms micelles and different liquid crystal phases depending on the temperature and composition. The fluorocarbon micellar structure induced by temperature or composition change and added fluorocarbon cosurfactant has been systematically studied. The SAXS data were analyzed by the indirect Fourier transformation (IFT) and the generalized indirect Fourier transformation (GIFT) depending on the volume fraction of the surfactant and complemented by plausible model calculations. The C8F17EO20 forms spherical type micelles above critical micelle concentration (cmc) in the dilute region. The micelle tends to grow with temperature; however, the growth is not significant on changing temperature from 15-75 degrees C, which is attributed to the higher clouding temperature of the surfactant (>100 degrees C). On the other hand, the micellar structure (shape and size) is apparently unaffected by composition (1-25 wt %) at 25 degrees C. Nevertheless, addition of fluorocarbon cosurfactant of structure C8F17SO2N(C3H7)(CH2CH2O)H (abbreviated as C8F17EO1) to the semidilute solution of C8F17EO20 (25 wt %) favors micellar growth, which finally leads to the formation of viscoelastic wormlike micelles, as confirmed by rheometry and supported by SAXS. The onset sphere-to-wormlike transition in the structure of micelles in the C8F17EO20/water/C8F17EO1 system is due to the fact that the C8F17EO1 tends to go to the surfactant palisade layer so that the critical packing parameter increases due to a decrease in the effective cross-sectional area of the headgroup. As a result, spherical micelles grow into a cylinder, which after a certain concentration entangle to form a rigid network structure of wormlike micelles. 相似文献
19.
Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture 总被引:1,自引:0,他引:1
Herm ZR Swisher JA Smit B Krishna R Long JR 《Journal of the American Chemical Society》2011,133(15):5664-5667
Selected metal-organic frameworks exhibiting representative properties--high surface area, structural flexibility, or the presence of open metal cation sites--were tested for utility in the separation of CO(2) from H(2) via pressure swing adsorption. Single-component CO(2) and H(2) adsorption isotherms were measured at 313 K and pressures up to 40 bar for Zn(4)O(BTB)(2) (MOF-177, BTB(3-) = 1,3,5-benzenetribenzoate), Be(12)(OH)(12)(BTB)(4) (Be-BTB), Co(BDP) (BDP(2-) = 1,4-benzenedipyrazolate), H(3)[(Cu(4)Cl)(3)(BTTri)(8)] (Cu-BTTri, BTTri(3-) = 1,3,5-benzenetristriazolate), and Mg(2)(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate). Ideal adsorbed solution theory was used to estimate realistic isotherms for the 80:20 and 60:40 H(2)/CO(2) gas mixtures relevant to H(2) purification and precombustion CO(2) capture, respectively. In the former case, the results afford CO(2)/H(2) selectivities between 2 and 860 and mixed-gas working capacities, assuming a 1 bar purge pressure, as high as 8.6 mol/kg and 7.4 mol/L. In particular, metal-organic frameworks with a high concentration of exposed metal cation sites, Mg(2)(dobdc) and Cu-BTTri, offer significant improvements over commonly used adsorbents, indicating the promise of such materials for applications in CO(2)/H(2) separations. 相似文献
20.
C P Casey S W Singer D R Powell R K Hayashi M Kavana 《Journal of the American Chemical Society》2001,123(6):1090-1100
Reaction of ([2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)CO)](2)H)Ru(2)(CO)(4)(mu-H) (6) with H(2) formed [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COH)Ru(CO)(2)H] (8), the active species in catalytic carbonyl reductions developed by Shvo. Kinetic studies of the reduction of PhCHO by 8 in THF at -10 degrees C showed second-order kinetics with Delta H(double dagger) = 12.0 kcal mol(-1) and Delta S(double dagger) = -28 eu. The rate of reduction was not accelerated by CF(3)CO(2)H, and was not inhibited by CO. Selective deuteration of the RuH and OH positions in 8 gave individual kinetic isotope effects k(RuH)/k(RuD) = 1.5 +/- 0.2 and k(OH)/k(OD) = 2.2 +/- 0.1 for PhCHO reduction at 0 degrees C. Simultaneous deuteration of both positions in 8 gave a combined kinetic isotope effect of k(OHRuH)/k(ODRuD) = 3.6 +/- 0.3. [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COSiEt(3))Ru(CO)(2)H] (12) and NEt(4)(+)[2,5-Ph(2)-3,4-Tol(2)(eta(4)-C(4)CO)Ru(CO)(2)H](-) (13) were unreactive toward PhCHO under conditions where facile PhCHO reduction by 8 occurred. PhCOMe was reduced by 8 30 times slower than PhCHO; MeN=CHPh was reduced by 8 26 times faster than PhCHO. Cyclohexene was reduced to cyclohexane by 8 at 80 degrees C only in the presence of H(2.) Concerted transfer of a proton from OH and hydride from Ru of 8 to carbonyls and imines is proposed. 相似文献