共查询到20条相似文献,搜索用时 31 毫秒
1.
Bruce D. James Dr. Jerzy Mrozinski Prof. Julia Klak Brian W. Skelton Allan H. White 《无机化学与普通化学杂志》2009,635(2):317-322
The crystal structures of tetrachloroferrate(III) complexes having stoichiometry (BH)+ [FeCl4]? (where B = isoquinoline and 4‐aminopyridine) were determined at 100 K. While weak interactions, particularly N–H···Cl hydrogen bonds, are evident in the structures, distances between the Fe(III) centers are quite long in both cases. The structure of the compound with B = quinoline was compared with that previously established at room temperature, and showed that neither solid‐solid nor magnetic phase transitions occurred in this temperature range. Magnetic measurements on the paramagnetic powders indicate weak antiferromagnetic interactions transmitted through the crystal lattice, giving rise to Néel temperatures that are significantly below 10 K. Comparisons are made with other characterized [FeCl4]? compounds having similar organic base cations, enabling clarification of the superexchange mechanism. 相似文献
2.
《Journal of Coordination Chemistry》2012,65(3):153-157
Abstract The EPR spectrum of N, N'-bis-(acetylacetone)ethylenediimino Cu(II), [Cu-en(acac)2], and N, N'-bis-(1,1,1-trifluoroacetylacetone)ethylenediimino-Cu(II), [Cu-en(tfacac)2], have been studied in doped single crystals of the corresponding Ni(II) chelate. The parameters in the usual doublet spin-Hamiltonian are found to be: Cu[en(acac)2], gz =2.183 ± 0.003, gx =2.047 ± 0.004, gy =2.048 ± 0.004, Az =204.8 × 10?4cm?1, Ax =31.5 × 10?4cm?1, Ay =27.1 × 10?4 cm?1, AzN= 12.8 × 10?4 cm?1 and AxN =AyN =14.3 × 10?4 cm?1: Cu[en(tfacac)2], gz =2.192 ± 0.002, gx =2.048 ± 0.004, gy =2.046 ± 0.004, Az =200.8 × 10?4 cm?1, Ax =31.1 × 10?4 cm?1, Ay =28.3 × 10?4 cm?1, AzN =12.8 × 10?4 cm?1 and AxN =AyN =14.6 × 10?4 cm?1. These parameters are related to coefficients in the molecular orbitals of the complex. It is found that the α-bonding is quite covalent and there is significant in-plane σ-bonding. From the nitrogen hyperfine structure it is determined that the hybridization on the nitrogen is sp2. 相似文献
3.
The interaction between trans-1,2-diaminocyclohexane-N, N, N', N'-tetraacetic acid (H1DCTA or H4Z) and Mn(II) and Ni(II) ions has been investigated. The formation constants of the hydrogen chelates (MHZ?), and of the normal chelates (MZ2?), have been measured at 20, 30 and 40°C, and an ionic strength of 0.10 (KNO3). The former was done by a titration technique and the latter by a mercury indicator electrode method. Enthalpy and entropy changes characterizing the formation of the normal chelates have been calculated at 25°C. 相似文献
4.
Novel Lithium Chloride Suzuki Phases, Li6MCl8 (M = Fe, Co, Ni) The hitherto unknown Suzuki phases Li6FeCl8, Li6CoCl8, and Li6NiCl8 ( cF 60) were prepared by fusing the binary chlorides. X-ray, DTA, and conductivity data as well as the infrared and Raman spectra are presented. The unit cell dimensions of the cubic (space group Fm3 m) halides are a = 1029.3, 1027.5, and 1023.5 pm, respectively. Li6FeCl8 and Li6CoCl8 undergo a reversible phase transition to disordered LiCl solid solutions at 275 and 355°C, respectively. The metastable nickel compound can only be prepared by quenching from about 560°C. The lithium chloride Suzuki phases are fast lithium ion conductors at elevated temperatures. The specific conductivities are 1.4 × 10?1, 1.5 × 10?1, and 6.9 × 10?2Ω?1 × cm?1 at 500°C, respectively. Whereas the i.r. spectra of the Suzuki phases only reveal a broad band, the Raman spectra exhibit the four group theoretically allowed modes as sharp scattering peaks, which are discussed in terms of the vibrational modes of this structure. 相似文献
5.
The Variable Reaction Behaviour of Base‐free Tris(trimethylsilyl)methyl Lithium with Trihalogenides of Earth‐Metals and Iron Base‐free tris(trimethylsilyl)methyl Lithium, Tsi–Li, reacts with the earth‐metal trihalogenides (MHal3 with M = Al, Ga, In and Hal = Cl, Br, I) primarily to give the metallates [Tsi–MHal3]Li. Simultaneous to this simple metathesis a methylation also takes place, mainly with heavier halogenides of Ga and In with excess Tsi–Li, forming the mono and dimethyl compounds Tsi–M(Me)Hal (M = Ga, In; Hal = I), Tsi–MMe2 (M = Ga), and the bis(trisyl)derivative (Tsi)2InMe, respectively and the main by‐product 1,3‐disilacyclobutane. Representatives of each type of compound have been isolated by fractionating crystallizations or sublimations and characterized by spectroscopic methods (1H, 13C, 29Si NMR, IR, Raman) and X‐ray elucidations. Reduction takes place, when FeCl3 reacts with Tsi–Li (1 : 3 ratio) in toluene at 55–60 °C, yielding red‐violet Fe(Tsi)2, 1,1,1‐tris(trimethylsilyl)‐2‐phenyl ethane and low amounts of Tsi–Cl. Fe(Tsi)2 is monomeric, crystallizes in the monoclinic space group C2/c and consists of a linear C–Fe–C skeleton with d(Fe–C) of 204,5(4) pm. 相似文献
6.
Tetrakis(triphenylphosphane-iminato)tantalonium hexachlorotantalate, [Ta(NPPh3)4]TaCl6. Synthesis, IR Spectrum, Crystal Structure, and ab initio Calculations of the [Ta(NPH3)4]+ Ion The title compound has been prepared by the reaction of tantalum pentachloride with Me3SiNPPh3 in acetonitrile, forming colourless moisture sensitive crystals, which were characterized by IR spectroscopy and by an X-ray structure determination (Space group P1 , Z = 4, 6479 observed unique reflections, R = 0.053. Lattice dimensions at 20°C: a = 1268.4(3), b = 2361.0(6), c = 2400.0(6) pm, α = 85.81(2)°, β = 87.47(3)°, γ = 87.27(3)°). The compound consists of two symmetry-independent cations [Ta(NPPh3)4]+ and anions TaCl6?, respectively. In the cations the tantalum atoms are surrounded in a distorted tetrahedral fashion by the four nitrogen atoms of the phosphane-iminato ligands. The TaN and PN bond lengths in both individuals correspond well with double bonds. According to twisting phenomena of the phenyl rings the TaNP bond angles are different in the two cation species. The investigation is supplemented by ab initio calculations of the [Ta(NPH3)4]+ ion. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(4):383-392
Abstract The crystal structure of trans-tetrakis(1,2-diazole)bisbromomanganese(II) was solved by direct methods using single-crystal X-ray (Mo-Kα) diffractometer data and refined to R = 0.054 for 1270 unique reflections with I > 2Δ(I). The compound crystallized from water as almost colourless, monoclinic prisms in space group C2/c (No. 15) with unit cell dimensions a = 14.208(2), b = 9.454(1), c = 15.015(3)Å,β = 118.68(1)°, Z = 4. The structure is formed from [(C3H4N2)4(Br)2Mn] molecular units held together through stacking of the 1.2-diazole rings approximately in the b-direction and weak van der Waals forces and hydrogen bonds. The coordination sphere around the Mn2+ ion is weakly distorted octahedral with two pairs of trans-positioned 1,2-diazole molecules at distances Mn-N(1) = 2.246(7) and Mn-N(3) = 2.229(6) Å, respectively, in the basal plane and the Br? ions occupying the apical positions at a distance Mn-Br(1) = 2.729(1)Å. The angles Br(1)-Mn-N(1), Br(1)-Mn-N(3) and N(1)-Mn-N(3) are 91.2(1). 89.6(1) and 87.8(2)°. respectively. The 1,2-diazole rings are practically planar, but slightly tilted (N(1) and N(3) containing rings are at angles of 89.9(3) and 86.4(3)° with respect to the basal coordination plane). The molecular units form columns in the b-direction. The molar magnetic susceptibilities, corrected for diamagnetism by Pascals constants, at 93–303 K show the compound to be of high-spin complex type with a Curie-Weiss equation X'M = 4.30/(T-3.3) and the reflectance spectrum in accordance with this shows only a very weak shoulder at 23500 cm?1 corresponding to the 6A1g ± 4T2g transition for the Mn2+ ion. The infrared spectrum shows an Mn-Br band at 715 and Mn-N bands at 680, 600 and 580 cm?1. The thermogravimetric (TG) curve shows the complex to release the 1,2-diazole molecules in two steps in accordance with the structure. 相似文献
8.
Inhaltsübersicht. PPh4{MoNCl3[N(SiMe3)2]} entsteht aus PPh4[MoNCl4] und N,N,N′-Tris-(trimethylsilyl)benzamidin in siedendem Dichlormethan in Form bernsteinfarbener Kristalle, die wir IR-spektroskopisch und durch eine röntgenographische Strukturanalyse charakterisiert haben. Raumgruppe P21/n, Z = 4, R = 4,3% für 5168 unabhängige beobachtete Reflexe. Die Gitterkonstanten betragen für ?65°C: A = 918,9; b = 2850,5; c = 1353,9 pm; β = 107,51°. Die Verbindung besteht aus PPh4+-Ionen und Anionen [MoNCl3[N(SiMe3)2]}–, in denen das Molybdänatom verzerrt tetragonal-pyramidal von dem Nitridoliganden in Apical-Position (r MoN = 165 pm), von drei Chloratomen und von dem N-Atom des Bis(trimethylsilyl)amido-Liganden (r MoN = 194 pm) umgeben ist. Das N-Atom des Amido-Liganden besitzt eine planare Umgebung. PPh4{MoNCl3[N(SiMe3)2]}, a Nitrido Amido Complex of Molybdenum (VI) PPh4{MoNCl3[N(SiMe3)2}] has been prepared by the reaction of PPh4[MoNCl4] with N,N,N′-Tris(trimethylsilyl)benzamidine in boiling dichloromethane, forming amber coloured crystals, which were characterized by their IR spectrum as well as by an X-ray structure determination. Space group P21/n, Z = 4, R = 0.043 for 5168 observed independent reflexions. The lattice dimensions are at ?65°C: A = 918.9; b = 2850.5; c = 1353.9 pm; β = 107.51°. The compound consists of PPh4+ ions and anions {MoNCl3[N(SiMe3)2]}– in which the complex molybdenum anion forms a distorted tetragonal pyramid with the nitrido ligand (r MoN 165 pm) in the apical position and the chlorine atoms along with the nitrogen atom of the amido ligand (r MoN 194 pm) in the basical positions. The N atom of the amido ligand has a planar geometry. 相似文献
9.
Matthias Westerhausen 《无机化学与普通化学杂志》1992,618(12):131-138
Tris[bis(trimethylsilyl)amido]zincates of Lithium and Calcium Calcium-bis[bis(trimethylsilyl)amide] and Bis[bis(trimethylsilyl)amido]zinc yield in 1,2-dimethoxyethane quantitatively Calcium-bis{tris[bis(trimethylsilyl)- amido]zincate} · 3DME. When THF is chosen as a solvent, the two reactants and the zincate form a temperature-independent equilibrium, whereas in benzene no reaction occurs. The tris[bis(trimethylsilyl)amido]zincate anion displays characteristic 13C{1H) and 29Si{1H] chemical shifts of 7 and ?8 ppm, respectively; the nature of the solvent, the cation and the complexating ligands don't influence the IR nor NMR data of the zincate anion and thus verify that [Ca(DME)3]2+ and {Zn[N(SiMe3 2]3}? appear as solvent separated ions, which is also confirmed by their insolubility in hydrocarbons. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(4):255-260
Abstract The EPR spectra of single crystals of 63Cu(II) doped N, N'-bis(salicylidene)ethylenediimine Ni(II), [Ni(sal)2en] and 7-methyl-N, N'-bis(salicylidene)ethylenediimine Ni(II), [Ni(7-me sal)2en] have been studied. The usual doublet spin-Hamiltonian parameters for the complexes have been found to be: Cu(II)[(sal)2en]; g z =2.192 ± 0.002; g x =2.046 ± 0.004; g y =2.049 ± 0.004; A z =201.0 × 10?4 cm?1; A x =29.3 × 10?4 cm?1; A y =31.3 × 10?4 cm?1; AN z =12.6 × 10?4 cm?1; A N x =14.5 × 10?4 cm?1; A N y =15.7 × 10?4 cm?1; A H z =6.3 × 10?4 cm?1; A H x =7.3 × 10?4 cm?1; A H y =7.9 × 10?4 cm?1; Cu(II)[(7-me sal)2en]; g z =2.189 ± 0.002; g x =2.037 ± 0.004; g y =2.046 ± 0.004; A z =203.0 × 10?4 cm?1; A x =36.9 × 10?4 cm?1; A y =22.7 × 10?4 cm?1; A N z =12.6 × 10?4 cm?1; A N x =13.3 × 10?4 cm?1; A N y =14.0 × 10?4 cm?1. Values of molecular orbital coefficients calculated for these complexes show that their bonding properties are similar to those of other compounds of this type. There is considerable covalency in the metal-ligand [sgrave]-bonds, and significant in-plane pi-bonding is present. 相似文献
11.
Reactions of Iron Trichloride with Trithyazyl Chloride. Crystal Structure of [S4N4Cl]+[FeCl4]? Iron trichloride reacts with (NSCl)3 yielding S4N4[FeCl4]2, S3N3Cl2[FeCl4] or S4N4Cl[FeCl4], depending on the reaction conditions. The i.r. spectra prove the presence of [FeCl4]? ions for all three compounds. The 57Fe-Mössbauer spectra show a slight quadrupole splitting at 80 K for S3N3Cl2[FeCl4] (ΔEQ = 0.42 mm · s?1) and S4N4Cl[FeCl4] (ΔEQ = 0.23 mm · s?1), which indicates a slight deformation of the FeCl4? tetrahedra. The crystal structure of S4N4Cl[FeCl4] was determined and refined with X-ray diffraction data (2549 independent reflexions, R = 0.026). S4N4Cl[FeCl4] crystallizes in the triclinic space group P1 with two formula units per unit cell. The lattice constants are a = 712, b = 911, c = 1006 pm, α = 76.5°, β = 83.8° and γ = 80.5°. The structure consists of the so far unknown [S4N4Cl]⊕ cations and slightly deformed FeCl4? ions. The [S4N4Cl]⊕ ion consists of a S4N4 ring built up of two nearly planar S3N2 fragments having a dihedral angle of 136°. The average SN bond length is 157 pm, the SCI bond length 214 pm. 相似文献
12.
The solvatochromic compound [Cu(tfmh)Me4en]ClO4 (tfmh? denotes the anion of 1,1,1-trifluoro-6-methyl-2,4-heptanedione) was prepared and its structure has been determined from three-dimensional X-ray diffraction data. The structure consists of discrete [Cu(tfmh)Me4en]+ monomeric units and perchlorate ions. The copper(II) ion is surrounded by the two nitrogen atoms of the diamine molecule and the two oxygen atoms of the β-dionato anion. The N,N,N′,N′-tetramethyl-1,2-diaminoethane, Me4en, coordinates as bidentate ligand through the nitrogen atoms and adopts the gauche conformation and λ configuration. The CuN2O2 chromophore is virtually planar. The compound crystallizes in the monoclinic system (space group P21/c) with a = 11.9520(2), b = 14.6600(2), c = 17.2240(4) Å, β = 135.72(2)°, Z = 4 and V = 2107.01(7) Å3. 相似文献
13.
《Journal of Coordination Chemistry》2012,65(8):1278-1284
Tris(trimethylsilyl)cyanurate, C12H27N3O3Si3 (1), has been synthesized and characterized by elemental analysis, IR, Raman, 13C and 29Si NMR, and thermogravimetric methods. The molecular and crystal structure has been determined by single crystal X-ray diffraction. This compound crystallized in space group P63/m (176), Z = 2 with a = 11.017(2), b = 11.017(2), c = 9.676(3) Å; α = 90°, β = 90°, γ = 120°. The geometry of the molecule is compared with tris(trimethylsilyl)cyamelurate. 相似文献
14.
Synthesis and Crystal Structure of Dimeric Dipyrazole Dipyrazolato Platinum(II), [Pt(pz)2(Hpz)2]2 The dimeric complex [Pt(pz)2(Hpz)2]2 (Hpz = pyrazole) is obtained in water from [Pt(Hpz)4]2+ and OH? or pz?. The colorless compound is insoluble in water. It decomposes at 191°C to form Pt(pz)2. [Pt(pz)2(Hpz)2]2 crystallizes in the monoclinic space group C2/c with the lattice constants a = 2 165.5, b = 972,0, c = 1 648.4 pm, β = 123.09°, Z = 4. Each Pt2+ ion is coordinated in a square-planar arrangement by two Hpz molecules and two pz? anions. The dimeric complex is formed by four symmetrical N? H? N bridges between the Hpz and pz? ligands of both Pt atoms causing a complete charge delocalization between the ligands. The complex has the symmetry C2 with two of the bridging H atoms lying on the symmetry axis. The Pt? N distances of 200 pm correspond to covalent single bonds. v(NH) is observed as broad absorption at 2 400 cm?1. 相似文献
15.
Chiraz Falah Habib Boughzala Ahmed Driss Tahar Jouini 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2457-2466
During the exploration of the K2O-Bi2O 3 -As2O5 system, single crystals of a new arsenate of trivalent bismuth, K3Bi5(AsO4) 6, were isolated by solid state reaction at 600°C. The title compound crystallizes in the monoclinic system, space group C2/c (N°15) with a = 18.257(2) Å, b = 7.260(1) Å, c = 20.130(4) Å, β = 119.86(1)°, and Z = 4. Its structure consists of a three-dimensional framework made up of AsO4 tetrahedra and BiO6 and BiO7 polyhedra sharing edges and corners, delimiting cavities wherein K+ ions reside. This compound exhibits a potassium ion conductivity but with rather low conductivity value. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(5):479-496
1-Alkyl-2-(arylazo)imidazoles (p-R-C6H4-N=N-C3H2N2X, abbreviated as RaaiX, R = H(a), CH3(b), Cl(c); X = N(1)-CH3 (1), N(1)-CH2-C6H5 (2)) have been reacted with (NH4)2[OsCl6] and OsCl2(RaaiX)2 species isolated in two isomeric forms, blue-violet (3, 5) and red-violet (4, 6). IR spectra show two x (Os-Cl) modes and support a cis-OsCl2 configuration. X-ray diffraction methods were used to determine structures of blue-violet isomers. In terms of the three coordination pairs around Os(II), Cl, Cl, N, N (N(imidazole), N) and N', N' (N(azo), N') the blue-violet isomers have a cis-trans-cis (ctc) configuration. 1H NMR data for the red-violet complexes (isomers B) and results concerning analogous ruthenium(II) complexes indicate isomer B to have cis-cis-cis (ccc) configuration. Absorption spectra show an intense MLCT band at ca 580 nm along with two weak bands at 800 and 1000 nm. Cyclic voltammetry shows quasi-reversible Os(III)/Os(II) and Os(IV)/Os(III) couples at 0.4-0.6 V and 1.3-1.5 V versus SCE and ill-defined azo reductions. The X-Ray structures show unusually long N=N bond lengths, 1.31-1.32 Å, elongated by some 0.06 Å compared to the free ligand value. Os(II) prefers to bind N(azo) (Os-N(azo), 1.98 Å) rather than N(imidazole) (Os-N(imidazole), 2.03 Å). EHMO calculations of ctc-OsCl2 (MeaaiMe) and comparison with the ruthenium(II) complex account for the MLCT transitions in terms of a metal-dominated HOMO to a ligand-dominated LUMO shift. 相似文献
17.
A. S. Platchinda M. Ranogajec-Komor A. Vértes 《Journal of Radioanalytical and Nuclear Chemistry》1972,10(1):89-94
The Mössbauer spectra of quenched aqueous iron(III) salt solutions containing HClO4, H2SO4, HCl, respectively, were measured. The magnetic hyperfine structure of the spectra was studied as a function of the change of acid and iron concentrations. In the solutions of FeCl3 containing 8.5N HCl we suppose the presence of octahedral [FeCl4(H2O)2]? complex. 相似文献
18.
Z. Warnke E. Styczeń D. Wyrzykowski A. Sikorski J. Kłak J. Mroziński 《Structural chemistry》2010,21(2):285-289
The crystal structure of tetraethylammonium tetrachloridoferrate(III) was determined. The crystals are hexagonal, space group P63 mc, a = 8.198(1) Å, b = 8.198(1) Å, c = 13.183(3) Å, V = 767.3(2) Å3, Z = 2. The asymmetric unit of [(C2H5)4N][FeCl4] consists of half each of a tetraethylammonium cation and a tetrachloridoferrate(III) anion. Tetrachloridoferrate(III) ion adopts almost ideal tetrahedral geometry. Structural characterization of the compound is supplemented by the results of its magnetic susceptibility measurements and electron paramagnetic resonance (EPR) spectra. Magnetic measurements of a powdered [(C2H5)4N][FeCl4] sample gave a negative Weiss constant of ?1.57, which suggests antiferromagnetic coupling. The susceptibility curve of [(C2H5)4N][FeCl4] against temperature exhibits a maximum, indicating the presence of antiferromagnetic ordering with a Neel temperature of approximately 2.9 K. 相似文献
19.
Acyl- and Alkylidenephosphines. XXVII. Molecular and Crystal Structure of Methyl-[(N-phenyl, N-trimethylsilyl)thiocarbamoyl]trimethylsilylphosphine . Methyl[(N-phenyl, N-trimethylsilyl)thiocarbamoyl]trimethylsilylphosphine 1a formed via an addition of methylbis(trimethylsilyl)phosphine to phenyl isothiocyanate [1], crystallizes in the monoclinic centrosymmetric space group P21/n with following dimensions of the unit cell determined at a temperature of measurement of ?80±3°C: a=1041.2(4);b=1706.9(12);c=1001.1(6)pm; β=106.41(4)°; Z = 4. An X-ray structure determination (Rw = 0.039) confirms the constitution of the compound as already derived from its nmr spectra. One trimethylsilyl group is bound to the phosphorus atom, whereas the other is connected with the sp2-hybridized nitrogen atom. Characteristic rounded bond lenghts and angles are: P? Si 231, P? CH3 184, P? C(S) 187, C?S 167, N? C(S) 137, and N? Si 181 pm as well as P? C? S 122°, P? C? N 117°, and S? C? N 121°. 相似文献
20.
A. N. Chekhlov 《Russian Journal of Coordination Chemistry》2009,35(3):222-225
A new complex [Cs(Db18C6)2]+[FeCl4]? was prepared and studied by X-ray diffraction (orthorhombic, space groupP21212,a = 22.934 Å,b= 24.024 Å,c= 16.665 Å,Z= 8; direct method, anisotropic full-matrix least-squares refinement,R= 0.087 for all 8800 independent reflections; CAD4 automated diffractometer, λMoK α. Two independent [FeCl4]? anions have a slightly distorted tetrahedral structure. Two independent host-guest type complex cations [Cs(Db18C6)2]+ have a sandwich structure. The Cs+ cation is located between two Db18C6 crown ligands below and above the centers of their 18-membered macrocycles and is coordinated by all 12 O atoms. The coordination polyhedron of Cs+ (C.N. 12) is a distorted hexagonal antiprism rotated toward a hexagonal prism. 相似文献