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911.
Preparation and characterization of the first derivatives of the fused macropolyhedral anion [B22H22]2− are reported. The species [B22H21OH]2− (1) and [B22H21OEt]2− (2) are obtained from workup of the products of the reaction between HgBr2 and [NBzlEt3]2[B22H22]; a cluster involving the conjoining of a closo-B12 icosahedron with a nido-B10 cluster. Washing the products with ethanol followed by thin-layer chromatography allows the isolation of 1 and 2, reproducibly, in yields of 27 and 20%, respectively. The species were characterized by NMR spectroscopy, elemental analysis and X-ray diffraction studies. The crystal structure determinations of the two species identify novel features. Apparently the influence of the O atoms in the ions [B22H21OH]2− and [B22H21OEt]2− results in the lengthening of what was a gunwale B---B connection adjacent to the junction of the two cages such that the distances are 2.180 and 2.230 Å, respectively. These latter are longer than the corresponding distance in the parent species [B22H22]2−, which is 2.09 Å; quite long for a normal B---B distance. Thus it is assumed that these B atoms, in 1 and 2, one of which bears the substituent, are not bonded to each other. 相似文献
912.
Mund G Vidovic D Batchelor RJ Britten JF Sharma RD Jones CH Leznoff DB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4757-4763
Several iron(III) complexes incorporating diamidoether ligands are described. The reaction between [Li(2)[RN(SiMe(2))](2)O] and FeX(3) (X=Cl or Br; R=2,4,6-Me(3)Ph or 2,6-iPr(2)Ph) form unusual ate complexes, [FeX(2)Li[RN(SiMe(2))](2)O](2) (2, X=Cl, R=2,4,6-Me(3)Ph; 3, X=Br, R=2,4,6-Me(3)Ph; 4, X=Cl, R=2,6-iPr(2)Ph) which are stabilized by Li-pi interactions. These dimeric iron(III)-diamido complexes exhibit magnetic behaviour characteristic of uncoupled high spin (S= 5/2 ) iron(III) centres. They also undergo halide metathesis resulting in reduced iron(II) species. Thus, reaction of 2 with alkyllithium reagents leads to the formation of iron(II) dimer [Fe[Me(3)PhN(SiMe(2))](2)O](2) (6). Similarly, the previously reported iron(III)-diamido complex [FeCl[tBuN(SiMe(2))](2)O](2) (1) reacts with LiPPh(2) to yield the iron(II) dimer [Fe[tBuN(SiMe(2))](2)O](2) but reaction with LiNPh(2) gives the iron(II) product [Fe(2)(NPh(2))(2)[tBuN(SiMe(2))](2)O] (5). Some redox chemistry is also observed as side reactions in the syntheses of 2-4, yielding THF adducts of FeX(2): the one-dimensional chain [FeBr(2)(THF)(2)](n) (7) and the cluster [Fe(4)Cl(8)(THF)(6)]. The X-ray crystal structures of 3, 5 and 7 are described. 相似文献
913.
The solid phase extraction as a solvent-free method for the analysis of oil and grease in waters was studied. The use of
a PTFE surface as a solid phase allows the retention of the volatile fraction of oil and grease, and further analysis of carbon–hydrogen
bonds using infrared spectroscopy can be done on the surface.
Various oils and grease samples were tested: n-hexadecane, n-tetradecane, n-nonadecane, n-docosane, isooctane, diesel oil
and gasoline. Temperatures from 25° to 90 °C and a range of heating times were checked for extraction.
Precision tests showed relative standard deviation values of around 10% in several samples of the same concentration. Calibration
lines of n-hexadecane showed high correlation coefficients from 0.9 to 30 mg/l. Recoveries for the various oils using different
calibration lines showed values from 90 to 110%.
The method described here is fast and clean, and allows reproducible measurements of oil and grease in water that do not require
the use of a solvent.
Received March 1, 2001; accepted August 15, 2001; published online July 15, 2002 相似文献
914.
A. I. Yarmolenko S. V. Kukharenko L. N. Novikova V. V. Strelets 《Russian Chemical Bulletin》1995,44(7):1300-1305
It has been shown by cyclic voltammetry in THF within the –90 to 40 °C temperature range that fluorenyl (5-9-R-C13H8)Mn(CO)3 complexes (R=But (3) and Ph (4)) undergo two-electron reduction to form allyl type [(3-9-R-C13H8)Mn(CO)3]2– dianions as final products. At low temperatures complexes3 and4 are reduced in two one-electron steps according to the EEC-scheme. The first step is reversible and corresponds to the formation of 19-radical anions 3–. and 4–.. TheE
0 values for redox pairs3
0/–. and4
0/–. are –1.88 and –1.73 V, respectively. The further reduction of radical anions3
–. and4
–. at more negative potentials is accompanied by fast 5 3 haptocoordination of the fluorenyl ligand to form 18-dianions [(3-9-R-C13H8)Mn(CO)3]2–. These dianions obtained by the reduction of complexes3 and4 by the radical anion of pyrene are stable at –80 °C and are characterized by their IR spectra. At room temperature the 5 3 hapticity change is a fast and reversible process occurring at the step of 19-radical anions3
–. and4
–. and leading to the electron deficient 17-species [(3-9-R-C13H8)Mn(CO)3]–., which are reduced easier than the initial complexes. As a result, complexes3 and4 are reduced to the corresponding dianions [(3-9-R-C13H8)Mn(CO)3]2– at room temperature in one reversible two-electron step according to the ECE-scheme. Reactivities of 19e–-species of the isomeric 5- and 6-fluorenylmanganesetricarbonyl complexes are compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1347–1353, July, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-05209) and the International Science Foundation (Grant No. REV 000). 相似文献
915.
The First Polyiodo Complex – Triethylsulfoniumtriiodomercurate(II)-tris(diiodine), (Et3S)[Hg2I6]1/2 · 3 I2 After Raman spectroscopic investigation of the system HgI2/Et3SIx, x = 3, 5, 7, triethylsulfoniumtriiodomercuratetris(diiodine), (Et3S)[Hg2I6]1/2 · 3 I2 was synthesized by reacting of HgI2 and liquid Et3SI7. The compound crystallizes at room temperature triclinically in the space group P1 with a = 879.4(7), b = 1 209.1(5), c = 1 291.5(5) pm, α = 96.16(3)°, β = 103.82(6)°, γ = 99.05(5)° and Z = 2. The crystal structure is composed of disordered Et3S+ cations, the centrosymmetric complex anion [HgI2/2I2]22? and three connecting iodine molecules I2. 相似文献
916.
Jorge Angulo Cornejo Ketty Ayala Rainer Richter Heinz Bhlig Lothar Hennig Lothar Beyer 《无机化学与普通化学杂志》2005,631(15):3040-3045
Hydrogen Bonds in 1,1‐Bis(2‐hydroxyethyl)‐3‐benzoylthiourea and its Nickel(II)‐ and Copper(II)‐Chelate Complexes The ligand 1,1‐bis(2‐hydroxyethyl)‐3‐benzoylthiourea HL, ( 1 ), yields with nickel(II) and copper(II) ions neutral complexes [NiL2], ( 2 ), and [CuL2], ( 3 ). By X‐ray structure analysis and IR spectroscopy different intramolecular hydrogen bonds (OH…O) and (OH…N) could be identified in both equally coordinated ligands of the [NiL2] molecule. For comparison X‐ray and IR data were also estimated for 1 and 3 . 相似文献
917.
Reyer J Dijkstra Hans F.M Boelens Freek Ariese Cees Gooijer 《Analytica chimica acta》2004,519(2):129-136
In column liquid chromatography (LC) coupled to conventional Raman spectroscopy (RS) removal of the spectral background of the eluent is often demanding, because of the strong signals of the organic modifier. A new chemometrical method is proposed, called the eluent background subtraction (EBS) method, which can correct for small shape and intensity differences of the eluent spectra. The variations in the eluent spectra are modelled using principal component analysis (PCA). The PCA loading vectors are subsequently used for eluent background correction of the elution spectra of the analyte. The loading vectors are fitted under these spectra by an asymmetric least-squares method. This method was successfully applied under various experimental conditions and performed much better than conventional background correction methods. Analyte detectability was improved by (weighted) averaging of all elution spectra and smoothing via a p-spline function. 相似文献
918.
When a benzene ring bears two 2-methyl-1-naphthyl moieties in the para, meta or ortho positions as in 1,4-bis(2-methyl-1-naphthyl)benzene, 1, 1,3-bis(2-methyl-1-naphthyl)benzene, 2 and 1,2-bis(2-methyl-1-naphthyl)benzene 3, two rotational isomers (atropisomers) are generated, with the two naphthyl substituents in a syn or anti relationship. In the case of the para and meta derivatives (1 and 2, respectively) these atropisomers could not be separated but were detected by NMR spectroscopy, that also allowed the determination of their syn-anti interconversion barriers in solution (19.5 and 20.4 kcal mol−1, respectively) and, in the case of 2, also in the solid state (26.7 kcal mol−1). In the more hindered ortho derivative 3, the syn (meso) and anti (racemic) atropisomers interconvert in solution with a barrier (31.2 kcal mol−1) sufficiently high to allow their physical separation. The racemic form could also be separated (by enantioselective HPLC) into the PP and MM enantiomers. Analysis of the corresponding CD spectra allowed the assignment of the absolute configuration. When three such naphthyl substituents are bonded to the phenyl in a meta relationship, two atropisomers in statistical proportions were observed: the anti (Cs symmetry) and the syn (C3v symmetry) display a 3:1 ratio at the equilibrium in solution. This ratio is different in the solid state, as is the interconversion barrier (22.1 and 32.1 kcal mol−1 in solution and in the solid, respectively). 相似文献
919.
920.
The nickel–iron alloy electrodeposition is affected by a superimposed magnetic field. Some previous papers [Msellak et al.,
Magnetohydrodynamics, 39:487–493, 2003 and Msellak et al., J Magn Magn Mat, 281:295–304, 2004] have exhibited some dramatic changes in iron amount and morphology of these deposits. As it is usual for a magnetic field
up to 1 T, no charge transfer effect can be expected, and the observed modifications can be explained by the magnetohydrodynamic
convection that controls the iron species flux during the electrochemical reaction. By electrochemical impedance spectroscopy
and physical investigations (scanning electron microscopy, X-ray diffraction, and inductively coupled plasma), the reduction
process is analyzed, the characteristic parameters of the mechanism are determined, and the magnetic field effects can be
quantified.
Contribution to special issue on “Magnetic field effects in Electrochemistry”. 相似文献