Vapour pressures and enthalpies of sublimation of the complexes (acac)M (olefin)2 and (acac)M(CO)2 (M = Rh(I), Ir(I); olefin = ethylene, propylene, vinyl chloride, vinyl acetate and methyl acrylate) were determined by the Koudsen effusion method. 相似文献
The infrared spectra, transmittance and polarized reflectance, of KNaSO4 and K3Na(SO4)2 are reported. Group theoretical analysis was carried out and a vibrational assignment proposed on basis of C3v and D3d symmetries. Factor group and site effects are discussed. 相似文献
Mass spectra of Fe3(CO)9X2 (X S, Se, Te) and Fe2(CO)6X′2 (X′ S, Se) are recorded and their fragmentation pattern given. The thermal decarbonylation has been studied using DTA/TG methods in the temperature range 25–600°C. The results are compared with those obtained from mass-spectroscopic studies. X-ray and magnetic measurements have been carried out on the residues obtained in the decarbonylation process. 相似文献
Cat2PMn(CO)5 (1, cat = ) is found to undergo carbonyl substitution reactions with phosphorus donors to give the isolable products cat2PMn(CO)4L, where L = cis-PPh3 (2); trans-PPh3 (3); cis-P(OMe)3 (4); and cis-P(OPh)3 (5). No evidence for CO insertion into the pentacoordinate PMn bond is observed. The X-ray crystal structure of 5 shows that the crystals are monoclinic, space group P21/n. The unit cell parameters are: a 10.523(2), b 25.765(5), c 13.344(2) Å, β 99.11(2)°, and Z = 4. Full matrix least squares refinement reached R= 0.054 for 3099 observed reflections. The pentacoordinate phosphorus adopts a distorted trigonal bipyramid geometry with the Mn in an equatorial position. Noteworthy is the small equatorial OPO angle of 110.1(2)°. 相似文献
Three-coordinate RhX(PCy3)2 complexes (X = F, Cl, Br, I; Cy = cyclohexyl) have been prepared from rhodium(I) cyclooctene compounds. RhCl(PCy3)2 is in equilibrium with its dimer. The complexes RhX(PCy3)2 (X = Cl, Br, I) form the adducts RhX(PCy3)2(N2) with dinitrogen, the times for N2-fixation being 4 days, 3 hours and 15 minutes respectively. The three-coordinate complexes form four-coordinate dioxygen adducts RhX(PCy3)2(O2) which have unusually high ν(OO) at about 990 cm?1. This high frequency is attributed to the four-coordination, which is exceptional for dioxygen complexes. From RhF(PCy3)2 carbonyl, ethene, and diphenylacetylene complexes RhX(PCy3)2L (X = F, Cl, Br, I, N3, NCO, NCS; L = CO, C2H4, C2Ph2) (X = CN, NO3, acetate; L = CO) have been prepared. The trans-influence of the anionic ligands on the infrared frequencies of the neutral ligands is discussed in terms of the different π-bonding properties of the X- and L-ligands. 相似文献
The polarized Raman spectra of small single crystals of Tl3Cr(SO4)3 have been recorded using the Raman microprobe technique in the temperature range 295–660 K. The behavior of the external modes is analyzed on polycrystalline samples with conventional Raman spectrometer from 100 K to the decompositon temperature 660 K. Analysis of the spectra, in connection with dielectric measurements and X-ray data show that Tl3Cr(SO4)3 undergoes the following space group phase sequence in accordance with the point group relationship 相似文献
The viscosities of Sr(NO3)2 and Cd(NO3)2 have been determined in dioxane, glycol and methyl alcohol+water mixtures at 10, 20 and 30% by weight. The B values have been computed at different temperatures both from the Jones—Dole and Das's equation. From the B values, the effective rigid molar volume, its change with % of organic solvent, temperature and the ion—solvent interaction have been inferred. Activation parameters have also been calculated and the structure breaking effect has been deduced. 相似文献
M(CO)5X (M = Mn, Re; X = Cl, Br, I) reacts with DAB (1,4-diazabutadiene = R1N=C(R2)C(R2)′=NR′1) to give M(CO)3X(DAB). The 1H, 13C NMR and IR spectra indicate that the facial isomer is formed exclusively. A comparison of the 13C NMR spectra of M(CO)3X(DAB) (M = Mn, Re; X = Cl, Br, I; DAB = glyoxalbis-t-butylimine, glyoxyalbisisopropylimine) and the related M(CO)4DAB complexes (M = Cr, Mo, W) with Fe(CO)3DAB complexes shows that the charge density on the ligands is comparable in both types of d6 metal complexes but is slightly different in the Fe-d8 complexes. The effect of the DAB substituents on the carbonyl stretching frequencies is in agreement with the A′(cis) > A″ (cis) > A′(trans) band ordering.Mn(CO)3Cl(t-BuNCHCHNt-Bu) reacts with AgBF4 under a CO atmosphere yielding [Mn(CO)4(t-BuNCHCHN-t-Bu)]BF4. The cationic complex is isoelectronic with M(CO)4(t-BuNCHCHNt-Bu) (M = Cr, Mo, W). 相似文献
The ion-solvent interaction of Sr(NO3)2 and Cd(NO3)2 in 10, 20 and 30 wt.% organic solvent (dioxane, glycol, methyl alcohol)-water mixtures at different temperatures has been studied using electrolytic conductivity data. The dissociation constant of the ion-pair Sr(NO3)+ and Cd(NO3)+ has been calculated along with ΔG0t, ΔG0t(cl) and ΔG0t(ch). The ion pairs interact with the solvents and the interaction is of the order dioxane+water>methyl alcohol+water>glycol+water. 相似文献
NaNi4(PO4)3 crystallizes in the space group Amam, a = 9.892(1), B = 14.842(2), and c = 6.3576(2) Å. For Z = 4, the calculated density is 3.862 g/cm3 (V = 933.3Å3). The presence of several weak reflections (of the class 2k0 and 6k0) which should be systematically absent in this space group has been attributed to a partial disorder of one of the phosphate tetrahedra. Two half-occupied P(2) sites related by a mirror normal to the a axis result in a column of phosphate tetrahedra pointing either up or down in this direction. Nickel atoms occupy five- and six-coordinated sites while sodium is six-coordinated. 相似文献
Vapour pressure measurements have been carried out on the complexes W(CO)it6-x (NCCH3x(x=1,2,3) and Mo(CO)it6-x(NCCH3x(x=1,3) employing the Knudsen effusion technique. The following enthalpies of sublimation, ΔH298sub(kJ mole?1), have been determined from vapour pressure data: W(CO)5(NCCH3)=98.1±2.0; W(CO) 4 (NCCH3)2=131.0±6.0; W(CO)3(NCCH33=103.4±6.0; Mo(CO)5(NCCH3)=105.8± 5.6; and Mo(CO)3(NCCH3)3=111.3±3.0. 相似文献
The vapour pressures and enthalpies of sublimation for a number of M(CO)5L-complexes (M = Cr, Mo, W and L = piperidine, pyridine, pyrazine, pyrazole, thiazole) have been determined by the Knudsen effusion method. The results are compared with similar complexes and dipole moment measurements from the literature. 相似文献
The complexes [Rh(η3-C3H4R)(η5-C5R′5)L]+BF4- (R 1-Me, R′ H, Me; R 2-Me, R′ H) (L C5H5N, Ph3P, Ph3As) have been prepared from Rh(η3-C3H4R)(η5-C5R′5)Cl and AGBF4 in acetone, followed by reaction with the stoicheiometric quantity of L. The 1H and 13C NMR spectra of the salts are reported and discussed. 相似文献
The structure of the compound Fe4(CO)12S(CSNMe2)(CNMe2) has been determined by X-ray crystallography. The compound crystallizes in space group P21/c with four molecules in a unit cell of dimensions a 8.840(2), b 20.174(9), c 16.856(5)Å, β 114.82(3)°. Full-matrix least-squares refinement of 2881 counter data yielded R = 0.046. The molecule consists of two Fe2(CO)6 units bridged by thiocarboxamido and immoniocarbene ligands and by a common bridging sulfur atom. The structure of this compound is compared with those of related molecules and a detailed comparison is made of the bonding properties of the thiocarboxamido ligand in bridging and chelating configurations. 相似文献
Cu4(PO4)2O crystallizes in the space group with a = 7.5393(8) Å, b = 8.1021(9) Å, c = 6.2764(8) Å, α = 113.65(1)°, β = 98.42(1)° and γ = 74.19(1)°. The structure was refined by full-matrix least-squares techniques using automatic diffractometer data to R = 0.046 (Rw = 0.056). Four unique copper atoms are in six, five-, and four-coordinated polyhedra which are linked together to form a three-dimensional network. The structure is best described in terms of a cubic close-packed array of oxygen atoms with one-tenth of the possible anion sites vacant. 相似文献
The thermal dissociation of the [Co(en)3](SCN)3 and [Co(en)3]I3 complexes was studied by thermogravimetry, differential thermal analysis, thermomagnetic analysis, pyrolytic techniques, evolved gas analysis, and mass spectrometry, in vacuo and nitrogen atmospheres. It was found that the [Co(en)3](SCN)3 complex dissociated in four steps: It was not possible to elucidate the intermediate compounds formed in the thermal dissociation of the [Co(en)3]I3 complex. 相似文献
(η4-enone)Fe(CO)2L complexes (enone = benzylideneacetone, cinnamaldehyde; L = PPh3-xMex (x = 0–2), P(OPh)3) exist as interconverting isomeric mixtures in solution in which L occupies either the axial or basal position of a square pyramidal structure. The ratio of isomers is dependent on the steric properties of both L and the enone. 相似文献
1'1,-Ferrocenediacetic acid anhydride has been prepared and it has been shown to be useful in the preparation of new heteroannularly substituted ferrocenyl-penicillins and -cephalosporins; these compounds exhibit antibiotic activity. 相似文献
AVX3 (A = Rb, Cs, (CD3)4 N; X = Cl, Br, I) crystallize in the hexagonal system, space group , with chains of face-sharing VX6 octahedra along the c-axis. This leads to a pronounced one-dimensional character of their magnetic properties with a strong antiferromagnetic exchange interaction J between nearest neighbor V2+ ions along these chains. All compounds except [(CD3)4N]VCl3 order three-dimensionally with ordering temperatures Tc between 13 and 32 K. In the ordered phase the magnetic moments, μ, lie in the basal plane in a triangular arrangement typical for antiferromagnetic interchain interaction J′. 相似文献
In the isomorphous hydrates MSO4 · H2O (M = Mn, Co, Ni, Zn), where M-OW distance is the only variable, the frequencies of the wagging, rocking and bending modes of water and of metal-oxygen stretching have been shown to correlate smoothly with the distance r(M-OW). Quantitative relations have been found for νW and ν(M-OW) which vary linearly, while νR and νC2 vary non-linearly with r(M-OW). 相似文献