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1.
Additives to MgB2 can improve the superconducting functional characteristics, such as critical current density (J c) and irreversibility field (H irr). Recently, we have shown that repagermanium (C6H10Ge2O7) is an effective additive, enhancing both J c and H irr. To look into details of the processes taking place during the reactive sintering, a thermal analysis study (0.167 K s?1, in Ar) is reported. We used differential scanning calorimetry between 298 and 863 K and simultaneous thermogravimetric—differential thermal analysis between 298 and 1233 K. Samples were mixtures of powders with composition 97 mol% MgB2 and 3 mol% C6H10Ge2O7. Up to 863 K, repagermanium decomposes by multiple steps and forms amorphous phases. A reaction with MgB2 is not observed. Above this temperature, partial decomposition of MgB2 occurs. Crystalline Ge and MgO are detected before formation of Mg2Ge and MgB4, when temperature approaches the melting point of Ge (1211 K). Carbon substitution for boron in the crystal lattice of MgB2 is observed for samples heated above 863 K. The amount of substitutional C does not significantly change with temperature.  相似文献   

2.
Reactions of Fe+ and FeL+ [L=O, C4H6, c-C5H6, C5H5, C6H6, C5H4(=CH2)] with thiophene, furan, and pyrrole in the gas phase by using Fourier transform mass spectrometry are described. Fe+, Fe(C5H5)+, and FeC6H 6 + yield exclusive rapid adduct formation with thiophene, furan, and pyrrole. In addition, the iron-diene complexes [FeC4H 6 + and Fe(c-C5H6)+], as well as FeC5H4(=CH2)+ and FeO+, are quite reactive. The most intriguing reaction is the predominant direct extrusion of CO from furan by FeC4H6 +, Fe(c-C5H6)+, and FeC5H4(=CH2)+. In addition, FeC4H 6 + and Fe(c-C5H6)+ cause minor amounts of HCN extrusion from pyrrole. Mechanisms are presented for these CO and HCN extrusion reactions. The absence of CS elimination from thiophene may be due to the higher energy requirements than those for CO extrusion from furan or HCN extrusion from pyrrole. The dominant reaction channel for reaction of Fe(c-C5H6)+ with pyrrole and thiophene is hydrogen-atom displacement, which implies DO(Fa(N5H5)+-C4H4X)>DO(Fe(C5H5)+-H)=46±5 kcal mol?1. DO(Fe+-C4H4S) and DO(Fe+-C4H5N)=DO(Fe+-C4H6)=48±5 kcal mol?1. Finally, 55±5 kcal mol?1=DO(Fe+-C6H6)>DO(Fe+-C4H4O)>DO(Fe+-C2H4)=39.9±1.4 kcal mol?1. FeO+ reacts rapidly with thiophene, furan, and pyrrole to yield initial loss of CO followed by additional neutral losses. DO(Fe+-CS)>DO(Fe+-C4H4S)≈48±5 kcal mol?1 and DO(Fe+-C4H5N)≈48±5 kcal mol?1>DO(Fe+-HCN)>DO(Fe+-C2H4)=39.9±1.4 kcal mil?1.  相似文献   

3.
With the aim of improving flux pinning and in-field critical current density [JC(H)], two physically and chemically different additives – burned rice husk (BRH) and nano Ho2O3 were introduced into in situ MgB2 superconductor. The effects of the above two additives were studied individually and combinedly. Ho2O3 decomposed and reacted with B to form HoB4, without any substitution. BRH caused considerable amount of C substitution at B site and formed Mg2Si and Mg2C3 secondary phases. Addition of Ho2O3 improved the JC(H) only marginally, but BRH improved the JC(H) strongly. Combined addition of Ho2O3 with BRH was found to be much more effective than their solo addition for the enhancement of JC(H) of MgB2.  相似文献   

4.
The diiron ynamine complexes [Fe2(CO)7{μ-C(R)C(NEt2)}] (1) (R=Me, Ph, C3H5, SiMe3) react with theN-sulfinylaniline, PhNSO, in refluxing hexane to yield the complexes [Fe2(CO)6{μ-N(Ph)C(Me)S}] (2), [Fe2(CO)6{μ-N(Ph)C(NEt2)C(Ph)S}] · 0.5C6H12 (3), [Fe2(CO)6{μ-C(C3H5)C(NEt2)N(Ph)SO}] · 0.5CH2Cl2 (4), and [Fe2(CO)6{μ-C(SiMe3)C(NEt2)S)}] (5). Compound 5 was found to be identical to the previously reported product obtained from the reaction of 1 with sulfur. Compounds 2, 3, and 4 were characterized by single crystal X-ray diffraction analyses. Crystal data: for 2: space group = P21/n,a=9.533(1) Å,b=18.830(4) Å,c=12.705(4) Å, β=107.01(2)°,Z=4, 2687 reflections,R=0.027; for 3: space group=P21/n,a=13.660(2) Å,b=19.096(8) Å,c=10.972(2) Å, β=90.62(1)°,Z=4, 2821 reflections,R=0.036; for 4: space group=P21/a,a=18.098(5) Å,b=16.564(4) Å,c=18.548(2) Å, β=115.44(2)°,Z=4, 3569 reflections,R=0.041. Complexes 2 and 3 result from fragmentation of theN-sulfinylaniline ligand and insertion of the nitrene grouping into the Fe=C(aminocarbene) bond, whereas the sulfur atom inserts into one Fe-C bond of the bridging carbene. Compound 4 is formed by insertion of the entireN-sulfinyl aniline ligand into the Fe=C(aminocarbene) bond. All three complexes have basket-like arachno structure isolobal to the benzvalene one.  相似文献   

5.
A new hybrid organic–inorganic material with the structural formula unit [La(H2O)4(m-PO3C6H4COOH)(m-PO2(OH)C6H4COOH)(m-PO(OH)2C6H4COOH)]2 (or [La(H2O)4C21H18O15P3]2) has been synthesized under hydrothermal condition from La(NO3)3·6H2O and 3-phosphonobenzoic acid (m-PO(OH)2–C6H4–COOH) which is a rigid organic precursor possessing two types of functional groups: phosphonic acid and carboxylic acid. The two units of the produced hybrid are linked together by hydrogen bonds leading to a layered framework composing of by a repetition of inorganic and organic slices. The organic layers consist of dimeric units made of two meta-phosphono-benzoic acid linked together by hydrogen bonds involving their COOH groups. Two kinds of dimeric units are observed: PO3C6H4COOH?HOOCC6H4PO(OH)2, present 2 times in the structure, and PO2(OH)C6H4COOH?HOOCC6H4PO2(OH). The material crystallises in a monoclinic cell (C2/c (15) space group) with the following parameters: a = 42.515(4) Å, b = 7.4378(6) Å, c = 20.307(2) Å, β = 118.031(6)°, V = 5668.2(9) Å3, Z = 4, density = 1.908 g/cm3.  相似文献   

6.
The organo-templated iron(III) borophosphate (C3H12N2)FeIII 6(H2O)4[B4P8O32(OH)8] was prepared under mild hydrothermal conditions (at 443 K) and the crystal structure was determined from single crystal X-ray data at 295 K (monoclinic, P21/c (No. 14), a=5.014(2) Å, b=9.309(2) Å, c=20.923(7) Å, β=110.29(2)°, V=915.9(5) Å3, Z=2, R1=0.049, wR2=0.107 for all data, 2234 observed reflections with I>2σ(I)). The title compound contains a complex inorganic framework of borophosphate trimers [BP2O8(OH)2]5− together with FeO4(OH)(H2O)- and FeO4(OH)2-octahedra forming channels with ten-membered ring apertures in which the diaminopropane cations are located. The magnetization measurements confirm the Fe(III)-state and show an antiferromagnetic ordering at TN≈14.0(1) K.  相似文献   

7.
The first observation of barriers to rotation about the CarylCcarbene bonds in aryl-substituted metal carbene complexes is reported. Using variable temperature 1H NMR, barriers of 9.1 and 10.4 kcal/mol have been determined for Cp(CO)2FeCHC6H5+ and Cp(CO)2FeCH(p-CH3C6H4)+, respectively. The data clearly indicate a geometry of the complex in which the aryl ring lies coplanar with FeCcarbeneCipso plane.  相似文献   

8.
The crystal structure of [HAlNCH(CH3)C6H5] 6·13 C6H14 has been determined by single crystal three-dimensional X-ray analysis. Block-matrix least-squares refinement led to conventional R factor of 0.08. The molecule is built up of a prismatic hexagonal framework, (AlN)6. Average AlN distances are 1.893(6) and 1.981(7) Å in the six-membered rings and in transverse bonds, respectively. Crystal data: hexagonal, space group P63, a 22.296(5), c 18.144(4) Å, V 7811.2 Å3, Z = 6, Dc 1.16 g cm?3.  相似文献   

9.
Nonacarbonylbis(μ3-phenylarsinidene)triiron(2FeFe) has been prepared by reaction of Na2[Fe(CO)4] with C6H5AsCl2. Its X-ray structural study reveals an Fe3As2 cluster. Three Fe(CO)3 groups occupy the equatorial positions of a distorted trigonal bipyramid with two μ3-bridging AsC6H5 groups at the axial sites. The Fe3 triangle contains only two FeFe bonds as reflected by different atomic distances.Crystal data: space group P21/c, a = 11.427(9), b = 15.43(1), c = 14.60(1) Å, β = 107.32(3)°, Z = 4. With 3786 reflections, for which Fo > 3(Fo), the structure has been refined anisotropically (hydrogen atoms isotropically) to R = 0.048.  相似文献   

10.
Molecular weight measurements and microwave titrations indicate that no interaction occurs between tetrameric 2-Me2NCH2C6H4Cu (Ar4Cu4) and the monodentate ligands PPh3, CH3CN or pyridine. However, the tetrameric structure Ar4Cu4 breaks down upon interaction (1/1 molar ratio ArCu/L) with the bidentate ligands (L) Diphos or cis-DPPEE to give the monomeric 1/1 complexes ArCu · L.Addition of Diphos to ArCu · Diphos or conducting the reaction of Ar4Cu4 with Diphos in a 1/2 ratio (ArCu/Diphos) gives rise to a CalkP bond cleavage reaction resulting in the formation of dimeric (Ph2PCu · Diphos)2 · 2 C6H6, ArH and Ph2PCHCH2.The molecular structure of (Ph2PCu · Diphos)2 · 2 C6H6, has been determined by a single-crystal X-ray diffraction study. Crystals are monoclinic, space group P21/c and have Z  2 in a unit cell of dimensions a  12.997(6), b  12.669(7), c  22.839(9) Å and β  94.48(4)°. The structure was refined to R  0.048 for 3048 independent reflections. The four copper atoms in the dimer are held together by two Ph2P bridges. The bonding in the dimer is discussed.  相似文献   

11.
The effect of SrII-for-BaII isovalent substitution on the magnetic irreversibility field (Hirr) of Cu(Ba1−ySry)2YbCu2O6.95(2) (Cu-1212) sample series (y=0-0.4) is studied to reveal guiding rules for tailoring the intrinsic Hirr characteristics of high-Tc superconductors. It has been assumed that substitution of the larger alkaline-earth cation, BaII, by the smaller, SrII, might improve the Hirr characteristics as a consequence of the decrease in the thickness of nonsuperconductive blocking block (BB). However, results of the present work show that Sr substitution rather depresses the Hirr characteristics of the Cu-1212-phase superconductors even though the thickness of BB decreases. Both the amount of excess oxygen and the overall positive charge are confirmed to remain constant upon the Sr substitution by wet-chemical and X-ray absorption near-edge structure analyses, respectively. However, from neutron diffraction data analysis, it is found that Sr substitution breaks the conductive CuO chains in BB by shifting part of the excess oxygen atoms from the characteristic b-axis lattice site to the a-axis site. This is believed to decrease the concentration of mobile holes in the BB, as supported by the results of TEP measurements. The lower Hirr(T) lines of the Sr-substituted samples may thus be attributed to the lower concentration of mobile holes in BB.  相似文献   

12.
《Microporous Materials》1997,8(3-4):103-112
Fe4F3(PO4)(HPO4)4(H2O)4(N2C3H12) (labelled ULM-15) was prepared hydrothermally (7 days, 453 K, autogenous pressure) in the presence of 1,3-diaminopropane as organic template. Its structure was determined by single crystal X-ray diffraction. ULM-15 is monoclinic (Space group C2/c (no 15)) with lattice parameters a = 24.176(1) , b = 14.558(1) , c = 7.186(1) , β = 102.3(1)°, V = 2470.8(3) 3, Z = 4. Its three-dimensional framework is constituted from corner-sharing FeX6 (X = O, F, H2O) octahedra and tetrahedral PO4 and HPO4 groups. The structure presents trans-chains of FeO4F2 octahedra related to ferric dimers [Fe2O8F2(H2O)2] by tetrahedral units. They delimit 16-membered rings channels along [001] in which the diprotonated amines are inserted. ULM-15 shows 3D antiferromagnetic behaviour below TN ≈ 22 K.  相似文献   

13.
New Syntheses and Crystal Structures of Bis(fluorophenyl) Mercury, Hg(Rf)2 (Rf = C6F5, 2, 3, 4, 6‐F4C6H, 2, 3, 5, 6‐F4C6H, 2, 4, 6‐F3C6H2, 2, 6‐F2C6H3) Bis(fluorophenyl) mercury compounds, Hg(Rf)2 (Rf = C6F5, C6HF4, C6H2F3, C6H3F2), are prepared in good yields by the reactions of HgF2 with Me3SiRf. The crystal structures of Hg(2, 3, 4, 6‐F4C6H)2 (monoclinic, P21/n), Hg(2, 3, 5, 6‐F4C6H)2 (monoclinic, C2/m), Hg(2, 4, 6‐F3C6H2)2 (monoclinic, P21/c) and Hg(2, 6‐F2C6H3)2 (triclinic, P1) are described.  相似文献   

14.
A series of 2,6-bis(imino)pyridyl iron(II) and cobalt(II) complexes [2,6-(ArNCMe)2C5H3N]MCl2 (Ar = 2,6-i-Pr2C6H3, M = Fe: 3a, M = Co: 4a; Ar = 2,4,6-i-Pr3C6H2, M = Fe: 3b, M = Co: 4b; Ar = 2,6-i-Pr2-4-BrC6H2, M = Fe: 3c, M = Co: 4c; Ar = 2,4-i-Pr2-6-BrC6H2, M = Fe: 3d, M = Co: 4d) has been synthesized, characterized, and investigated as precatalysts for the polymerization of ethylene in the presence of modified methylaluminoxane (MMAO). The substituents of pyridinebisimine ligands and their positions located significantly influence catalyst activity and polymer property. It is found that the catalytic activities of the iron complexes/MMAO systems are mainly dominated by electronical effect, while those of the cobalt complexes/MMAO systems are primarily controlled by hindering effect.  相似文献   

15.
The crystal and molecular structure of the complex containing cobalt-carbon and iron-sulfur cluster cores, (μ-p-CH3C6H4C2S) (μ-n-C3H7S)Fe2(CO)6Co2(CO)6, has been determined by X-ray diffraction method. The crystals are triclinic, space group P&1bar;, with a — 9.139(2), b=9.610(1), c-17.183(2) Å, α = 84.36(1), β-89.45(1), γ=88.15(1)°, V-1501.0 Å3; Z=2, Dc=1.74 g/cm3. R=0.072, Rw=0.081. The results of the structure determination show a cobalt-carbon cluster core formed through the reaction of (μ-p-CH3C6H4C2S)(μ-n-C3H7S)Fe2(CO)6 with Co2(CO)8. In the cobalt-carbon cluster core, the bond length of the original C≡C lengthened to 1.324 Å which is close to the typical value of carbon-carbon double bond. The groups connecting the carbons of the cluster core are in cis position and lie on the opposite side of cobalt atoms. In this complex, the conformation of —SC3H7 is e-type, while that of —SC2C6H4CH3 is a-type.  相似文献   

16.
The cluster compounds (μ3-S)(μ3-PR)Fe3(CO)9 are obtained by reaction of the dichloroorganylphosphane sulphides RP(S)Cl2 (R = CH3, 4-CH3OC6H4, C6H5) with Na2[Fe(CO)4] in ether under cleavage of the PS bond. On the basis of X-ray crystallographic determinations the iron clusters crystallize for R = 4-CH3OC6H4 and C6H5 in the monoclinic and triclinic space group C2/c and P1 with Z = 8 and 4, respectively.  相似文献   

17.
The title compound, Cp2TiR (Cp=C5H5; R=2,6-(4-MeC6H4)2C6H3), 1, was prepared by reaction of RLi with [Cp2TiCl]2. Compound 1 was characterized by elemental analysis, EPR, and single crystal X-ray crystallography. The title compound crystallizes in the monoclinic space group C2/c with the following unit cell dimensions: a=11.1466(7) Å, b=16.4429(11) Å, c=13.0786(8) Å; b=106.2040(10)°;V=2301.9(3) Å3. The EPR spectrum of 1 displays two signals, a high field signal at g=1.979 and a lower field signal at g=1.959. Significantly, 1 is a sterically encumbered m-terphenyl-stabilized trivalent titanocene paramagnetic complex and may be a practical one-electron reducing reagent.  相似文献   

18.
Reactions of reactive cyclopentadienyliron complexes C5H5Fe(CO)2I, [C5H5Fe(CO)2THF]BF4, [C5H5Fe(CO)((CH3)2S)2]BF4 and [C5H5Fe(p-(CH3)2C6H4)]PF6 with P(OR)3 as ligands (R = CH3, C2H5, i-C3H7 and C6H5) lead to the formation of the complex compounds C5H5Fe(CO)2?n(P(OR)3)nI and [C5H5Fe(CO)3?n(P(OR)3)n]X (n = 1, 2 and n = 1–3, X = BF4, PF6). Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase of electron density on the central metal with increasing substitution of CO groups by P(OR)3 ligands. The stability of the compounds increase in the same way.  相似文献   

19.
The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2, has been accomplished by the reaction of NaMn(CO)5 with (CH3)3SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry P21c and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C6H5)3 bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C6H5)3 bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor.  相似文献   

20.
Fe(VI) batteries based on unusual ferrate cathodic charge storage have been studied for quite a few years. So far, a class of Fe(VI) compounds have been successfully synthesized and studied as the cathodic materials in both alkaline and nonaqueous battery systems. This paper provides a summary of the syntheses of a range of Fe(VI) cathodes including the alkali Fe(VI) salts Li2FeO4, K x Na(2?x)FeO4, K2FeO4, Rb2FeO4, Cs2FeO4, as well as alkali earth Fe(VI) salts CaFeO4, SrFeO4, BaFeO4, and a transition metal Fe(VI) salt Ag2FeO4. Two synthesis routes summarized in this paper are the solution phase synthesis and the solid-state synthesis. Preparation of coating-stabilized (coated with KMnO4, SiO2, TiO2, or ZrO2) Fe(VI) cathodes and preparation of thin-film reversible Fe(VI/III) cathodes are also presented. Fe(VI) analytical methodologies summarized in this paper include Fourier transform infrared spectrometry, titrimetric (chromite), ultraviolet-visible spectroscopy, X-ray diffraction, inductively coupled plasma spectroscopy, Mössbauer spectrometry, potentiometric, galvanostatic, and cyclic voltammetry. Cathodic charge transfer of Fe(VI) is also briefly presented.  相似文献   

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