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1.
Summary Complexes of general formula MLmCl2 · nH2O, where M=cobalt(II) or nickel(II); L=2-(4-methyl, 2-pyridyl)-benzimidazole (mpbi), 2-(4-methyl, 2-pyridyl)benzothiazole (mpbt), 2-(4-methyl, 2-pyridyl)benzoxazole (mpbo), 2-(4-methyl, 2-quinolyl)benzoxazole (mqbo), or 2-(4-methyl, 8-quinolyl)benzoxazole (mqbo); m=1,2; n=0–3, were prepared and characterized by t.g.a., conductance and magnetic measurements, i.r. and diffuse-reflectance electronic spectra.All the ligands behave as bidentate and coordinate through the pyridine- and isoxazole-nitrogen atoms.The nickel complexes have distorted octahedral or fivecoordinate structures. The cobalt complexes arepseudo-tet- rahedral except Co(mpbo)2Cl2·2H2O where the metal is six-coordinate.  相似文献   

2.
The structure of 1-(3,5-dimethyl-2-furyl)-3-(p-tolyl)-prop-2-en-1-one, C16H16O2 is determined by single-crystal x-ray diffractometry. Crystals are triclinic, , a=7.381(7), b=8.871(5), c=10.745(13) Å, =93.53(7), =102.25(8),=95.43(7)°, V=682(1) Å3, Z=2, dcalc=1.170 g cm–3, (Cu K)=1.54178 Å,=5.697 cm–1, M=270.30, F(000)=256, R=0.077 for 1601 unique observed reflections. The trans-geometry of the C=C double bond, thes-cis-geometry of the C=C-C=O moiety, and thes-trans arrangement of the carbonyl and furane oxygen atoms are proved.  相似文献   

3.
Oxidation of 2-(2-hydroxyethyl)pyridine (pyeol) to 2-pyridylacetaldehyde (pyeal) by CrVI has been studied in the 0.5–2.0M HClO4 range at I=2.2M and in super acidic media within the 3–7M HClO4 range. In all cases the reaction has been examined under pseudo-first order conditions keeping the alcohol and H+ aq in excess. CrIII-complexes formed during reduction of CrVI by pyeol at different molar ratios of the reactants, were isolated chromatographically and identified as [Cr(H2O)6]3+ and [Cr(pyeac)(H2O)4]2+ ions (pyeac=2-pyridylacetic acid). Free 2-pyridylacetaldehyde (pyeal) was separated and determined as its 2,4-dinitro-phenylhydrazone derivative. A dependence of the rate constants on [pyeol] and [H+] has been established at I=1.2M and I=2.2M. The apparent activation parameters at [H+]=1 and 2M have been determined. A rate law of the form d[CrVI]/dt= (k 1[H +]+k 2[H +]2)[pyeol][CrVI] is proposed. A linear dependence of log k obs on H0 in the super acidic media is obeyed. A rate decrease is observed if oxygen instead of argon is in the reaction cell. The reaction mechanism has been discussed.  相似文献   

4.
Mixed ligand complexes involving four aminoacid dithiocarbamates (RRdtc=glydtc (R=H; R=H), methdtc (R=H; R=C3H7S), sardtc (R=Me; R=H), trydtc (R=H; R=C9H8N), substituted phosphines [PPh3, Ph2PCH2CH2PPh2(dppe)] and nickel(II) are reported. All are diamagnetic. Thermal analyses of the complexes are in keeping with the proposed formulae. Thermal decomposition of the dithiocarbamate moiety proceeds through the formation of Ni(SCN)2. PPh3 and dppe are lost in the initial decomposition stages.  相似文献   

5.
Summary Cobalt(II) and nickel(II) halide complexes of the ligands 2-(2-methyl-8-quinolyl)benzoxazole (mqbo), 2-(2-methyl8quinolyl)benzimidazole (mqbi) and 2-(4-methyl-8-quinolyl)benzimidazole (mqbi) were synthesized and characterized by analytical, thermogravimetric, conductivity and magnetic data, and i.r. and electronic spectra.The ligands are bidentate N-donors yielding complexes where the coordination geometry depends on the metal ion and steric hindrance. All the cobalt complexes have formula [CoL2X2] and distorted tetrahedral geometry. Different types of nickel compounds were obtained: i) complexes of formula NiLX2 · n H2O (or EtOH) (L = mqbo or mqbi; n=0–1.5) which arepseudo-tetrahedral or five-coordinate and ii) complexes NiL2X2 · n H2O (L = mqbi, n=3 or 4) where the metal is bound to four nitrogen atoms and the overall coordination geometry is tetragonal. The structural changes occurring after removal of water or alcohol from the complexes are also reported.  相似文献   

6.
Summary TheSchiff base ligands 3-[(2-benzotrifluoride)-2-hydroxy-3H-naphth-3-ylidene)-methyl] aldamine (1) and 3-[(3-benzotrifluoride)-2-hydroxy-3H-naphth-3-ylidene)-methyl] aldamine (2) and their corresponding Cu(II) complexes (I, II) were synthesized. The crystal structures ofbis-{(2-benzotrifluoride)-[(2-oxo-3H-naphth-3-ylidene)]-methyl]-aminato} Copper(II) (I) andbis-{(3-benzotrifluoride)-[(2-oxo-3H-naphth-3-ylidene)-methyl]-aminato} Copper(II) (II) were determined. CompoundI crystallizes in the triclinic crystal system (a=12.561(3),b=16.211(4),c=8.007(2) Å, =96.29(2), =101.42(2), =97.10(2)°, space group ,Z=2); compoundII crystallizes in the monoclinic crystal system (a=5.064(2),b=19.172(4),c=15.111(3) Å, =95.05(2)°, space group P21/c,Z=2). The X-ray diffraction study shows that the geometry around the metal atom is square planar for both copper complexes.
Kristallstruktur vonbis-{(2-Benzotrifluorid)-[(2-oxo-3H-naphth-3-yliden)-methyl]-aminato}-Kupfer(II) undbis-{(3-Benzotrifluorid)-[(2-oxo-3H-naphth-3-yliden)-methyl]-aminato}-Kupfer(II)
Zusammenfassung DieSchiffschen Basen 3-[(2-Benzotrifluorid)-2-hydroxy-3H-naphth-3-yliden)-methyl]-aldamin (1) und 3-[(3-Benzotrifluorid)-2-hydroxy-3H-naphth-3-yliden)-methyl]-aldamin (2) sowie ihre entsprechenden Cu(II)-Komplexe (I,II) wurden synthetisiert und ihre Struktur im Kristall bestimmt. VerbindungI kristallisiert triklin (a=15.561(3),b=16.211(4),c=8.007(2) Å, =96.29(2), =101.42(2), =97.10(2)°, Raumgruppe ,Z=2); VerbindungII kristallisiert monoklin (a=5.064(2),b=19.172(4),c=15.111(3) Å, =95.05(2)°, Raumgruppe P21/c,Z=2). Aus der Röntgenstrukturanalyse ergibt sich eine quadratisch planare Geometrie der Komplexe.
  相似文献   

7.
The preparations of the nickel-morpholine (Morph) complexes Ni(NO2)2·3Morph and Ni(ClO4)2·4Morph·2H2O are described. The thermal treatment of this perchlorate and of NiSO4·2Morph led to the isolation of Ni(ClO4)2·2Morph·2H2O and NiSO4·Morph. The magnetic moments, diffuse reflectance spectra and infrared spectra of these compounds are all compatible with a pseudo-octahedral environment around the nickel atom.
Zusammenfassung Die Darstellung der Nickel-Morpholin(Morph)-Komplexe Ni(NO2)2·3Morph und Ni(ClO4)2·4Morph·2H2O wird beschrieben. Die thermische Behandlung dieses Perchlorates und von NiSO4·2Morph ergibt Ni(ClO4)2·2Morph·2H2O und NiSO4Morph. Magnetisches Moment sowie diffuse Reflektionsspektren und Infrarotspektren dieser Verbindungen sind kompatibel mit einer pseudooktaedrischen Koordination des Nickelatoms.

, () : Ni(NO2)2·, NiSO4·2 Ni(ClO4)2·4·2H2O. NiSO4· Ni(ClO4)2·2·2H2O. , , .


The authors are indebted to Consejeria de Cultura y Educación de la Comunidad Autónoma de Murcia for financial support.  相似文献   

8.
Summary Dichloro complexes of PdII, [Pd(L–L)Cl2], where L–L=1-(thiomethyl)-2-(diphenylarsino)ethane (S–As) or 1-(thiomethyl)-2-(diphenylphosphino)ethane (S–P) andtrans-[PdL2Cl2], where L=diphenyl(2-phenylethyl)-phosphine (PE), diphenyl(1-naphthyl)phosphine (PN) orN-methyl-2-thiophenealdimine (SN), have been prepared and characterized. The reactions of these complexes with MeLi were investigated. The dimethyl complexes [Pd(L–L)Me2] (L–L=S–As, S–P) and [Pd(PE)Me2] were isolated and characterized. Reaction of [Pd(L–L)Me2] (L–L=S–As, S–P) with HCl affords the monomethyl derivatives [Pd(L–L)Me(Cl)]. In contrast to the Pt analogues, [Pd(L–L)Me2] and [Pd(L–L)Me(Cl)] are relatively less stable than [Pt(L–L)Me2] and [Pt(L–L)Me(Cl)].  相似文献   

9.
Summary The crystal structure of the dimeric [{Ni(C15H11N3)(NCO)(H2O)}2](PF6)2 has been determined by x-ray diffraction methods. Crystal data are as follows: P 1,a=11.904(4) Å,b=10.392(4) Å,c=8.531(3) Å, =111.87(2)o, =90.61(3)o, =107.37(5)o, U=926.7(4) Å3, Z=2, Dm=1.77(2), Dx=1.78 g. cm–3, (Mo-K)=12.1 cm–1, F(000)=494. Least-squares refinement of 1230 reflections with I1.5(1) gave a final R =0.035 (R=0.038). The structure is formed by cationic [{Ni(C15H11N3)(NCO)(H2O)}2]2+ and anionic PF 6 units, linked through hydrogen bonds between the water molecule and the hexafluorophosphate ion. The resulting coordination geometry around each nickel(II) ion is ferragonally elongated octahedral. The N-bridging cyanate groups occupy simultaneously an equatorial position in the coordination sphere of one of the nickel atoms and an axial position in the other. The remaining axial positions are occupied by the water molecules. Powder susceptibility data, between 2.0 and 300 K, show the existence of ferromagnetic exchange between nickel centres. The magnetic parameters are J/K=6.6K, D/K =–17.6 K, zJ/K=0.57 and g-2.21.  相似文献   

10.
Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H2O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H2O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.  相似文献   

11.
The Dinitrone 2,2-diphenyl-3,3-bi-3H-indole-1,1-dioxide acts as a demethylating and dehydrogenating agent. The mechanism of interaction of the dinitrone with donors and acceptors does not involve intermediate charge-transfer complexes probably due to a self association between dinitrone molecules (as supported by X-ray determinations). The crystal structure of the dinitrone was obtained by direct methods;a=9.967 (2),b=19.817 (3),c=10.875 (2) Å, =111.2 (2)°, space group P21/n. The finalR andR w were 0.089 and 0.063 for all measured reflexes.
2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid: Molekulare Wechselwirkungen und Kristallstruktur
Zusammenfassung Das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid wirkt als Demethylierungs- und Oxydationsmittel. Die Wechselwirkung des Dinitrons mit Elektronen-Acceptoren und Elektronen-Donatoren geht wegen der Selbstassoziation zwischen den Dinitron-Molekülen ohne die dazwischenliegende Bildung eines Charge-Transfer-Komplexes vor sich; das wird auch von Röntgenstrukturuntersuchungen gestützt. Die Kristallstruktur wurde mit direkten Methoden ermittelt:a=9.967 (2),b=19.817 (3),c=10.875 (2) Å; =111.2 (2)°. P21/n. Die endgültigen WerteR undR w waren 0.089 und 0.063 für alle gemessenen Reflexe.
  相似文献   

12.
Summary. Zr5Ir2In4 was synthesized by reaction of the elements in a glassy carbon crucible in a water-cooled sample chamber of an induction furnace. The sample was characterized by X-ray diffraction on both powder and single crystals. Zr5Ir2In4 crystallizes with a pronounced Lu5Ni2In4 type subcell, space group Pbam, a=1739.5(6), b=766.3(2), c=338.9(2) pm. Weak additional reflections force a doubling of the subcell c axis. The superstructure of Zr5Ir2In4 is of a new type: Pnma, a=1739.5(6), b=677.8(2), c=766.3(2) pm, wR2=0.0529, 1592 F2 values, and 60 variable parameters. The group-subgroup scheme for the klassengleiche symmetry reduction is presented. The formation of the superstructure is most likely due to a puckering effect (size of the iridium atoms). The crystal chemistry of Zr5Ir2In4 is briefly discussed.  相似文献   

13.
Simultaneous TG/DTG/DTA studies under non-isothermal conditions have been carried out in air and nitrogen on some halo-dithiocarbamates of the general formula XM[S2CN(CH2)5]2 (X=Cl, Br and I; andM=As, Sb and Bi).E* values for the 1st stage of decomposition were determined by graphical methods and the TTN temperatures were calculated from the TG profiles. A possible mechanism of the decomposition reaction is suggested, based on the thermoanalytical and pyrolysis results and the mass spectral data. The kinetic analysis data on five of the above dithiocarbamates and nine complexes of the general formula M[S2CN<]3 (M=As, Sb and Bi; and N<=NEt2, N(CH2)5 and N(CH2)4O) were studied by the QIA (quasi-isothermal analysis) technique in air atmosphere. An example of kinetic parameter (k andn) estimation for the first decomposition stage is given for Bi[S2CN(CH2)5]3, with the assumption of different kinetic equations.
Zusammenfassung Einige helo-Dithiocarbamate der allgemeinen Formal XM[S2CN(CH2)5]2 (X=Cl, Br und I;M=As, Sb und Bi) wurden mittels simultaner TG/DTG/DTA unter nichtisothermen Bedingungen in Luft und Stickstoff untersucht. Für den ersten Zersetzungsschritt wurden E*-Werte durch graphische Methoden bestimmt und die TIN-Temperaturen aus den TG-Profilen berechnet. Ein auf den Ergebnissen der Thermogravimetrie und Pyrolyse sowie auf massenspektroskopischen Daten beruhender möglicher Mechanismus wird vorgeschlagen. Fünf der angeführten Dithiocarbamate und 9 Komplexe der allgemeinen Formel M[S2CN<]3] (M=As, Sb und Bi;N=NEt2, N(CH2)5 und N(CH2)4O) wurden mittels QIA (quasi-isotherme Analyse) in Luft untersucht. Als Beispiel ist die Bestimmung der kinetischen Parameter (k undn) für den ersten Schritt der Zersetzung von Bi[S2CN(CH2)5]3 unter Annahme verschiedener kinetischer Gleichungen angegeben.

, - XM[S2CN(CH2)5]2, =Cl, r l, a M=As, Sb Bi. a , -. - . M[S2CN<]3, M=As, Sb Bi, a N<=NEt2, N(CH2)5 N(CH2)4O. k 3[S2N(2)5]3.
  相似文献   

14.
Summary A quantum mechanical calculation of cross sections for the reaction F+H2(v=0,j=0) FH(vj)+H has been performed on the T5A semiempirical potential surface using hyperspherical coordinates. State-to-state integral and differential cross sections converge rapidly with the number of components of the total angular momentum projection onto the axis of least inertia. Thev=3 differential cross section has a forward peak whose magnitude increases with energy whereas thev=2 differential cross section has a backward maximum, in qualitative agreement with cross-beam experiments. Thev=2 andv=3 rotational distributions are in rather good agreement with experiment, but not the vibrational branching ratios.  相似文献   

15.
Four transition-metal carboxylate-like complexes have been synthesized from the reaction of the tertiary phosphine betaine triphenylphosphoniopropionate, Ph3P+(CH2)2CO 2 , with Co(ClO4)2· 6H2O, Cu(ClO4)2·6H2O, Cu(BF4)2·xH2O, and AgClO4, respectively, and fully characterized by single-crystal X-ray analysis. [CoPh3P(CH2)2CO2 4(H2O)2](ClO4)2·2H2O, 1, space groupP¯ l witha=9.195(2),b=13.000(2),c=18.795(3) Å,=102.52(1),=90.12(1),=109.28(2)° andZ=1; [CuPh3P(CH2)2CO2 4][Cu2 -Ph3P(CH2)2CO2 -O,O 4(H2O)2] (ClO4)6· 4H2O, 2, space groupP2l/c witha=14.225(3),b=24.624(6),c=24.297(5) Å,=94.18(1)°, andZ=2; [CuPh3,P(CH2)2CO2Me2N(CH2)2NMe2(H2O)2](BF4)2,3, space groupP2l/c witha=17.668(2),b=13.454(3),c=15.876(2) Å,=116.45(1)°, andZ=4; [Ag2Ph3P(CH2)2CO2 2(ClO4)]2(ClO4)2,4, space groupP¯ l witha=10.925(2),b=13.110(3),c=18.795(3) Å,=82.93(3),=87.45(3),=67.49(3)°, andZ=2. In complex1, the cobalt(II) atom is located in an inversion center and coordinated by four unidentate betaine ligands and a pair oftrans aqua ligands, and strong hydrogen bonds are formed between the aqua ligands and the pendant oxygen atoms of the betaine ligands. In complex2, mononuclear and dinuclear cations coexist in the asymmetric unit. In the mixed-ligand complex3 the betaine ligand acts in the unidentate coordination mode andN,N,N,N-tetramethylethylenediamine (tmen) in the chelate mode. Complex4 contains a discrete centrosymmetric tetranuclear cations in which one pair of betaine ligands act in the bidentate bridging mode and the other in both bidentate and one-atom bridging modes.  相似文献   

16.
An X-ray—diffraction study is reported for two molecular complexes containing 3,4-diamino-1,2,5-oxadiazole as guest (G) with 18-crown-6 (18-C-6) andcis-anti-cis-dicyclohexano-18-crown-6 (DCH-6B) as host. Both complexes are of the polymeric-chain structure with the guest molecule bridging two crown neighbours. ComplexI: [18-C-6*G*H2O], 111, monoclinic,P21/n,a=8.171(1),b=15.042(2),c=16.209(6) Å, =101.15(2)°, finalR-factor 0.068. ComplexII: [DCH-6B*G], 11, monoclinicC2/c,a=21.212(4),b=9.380(2),c=13.049(3) Å, =108.61(3)°, finalR 0.047.  相似文献   

17.
Rogers  Donald W.  Kim  Jae-Ha 《Mikrochimica acta》1986,90(3-4):259-266
An empirical equation H s, m=0.84n gives the enthalpy of solution of 30 branched, linear and cyclic alkanes in glacial acetic acid. The parametern is an effective carbon number which expresses the number of carbon atoms in the longest chain plus one half of the pendant methyl groups.  相似文献   

18.
An X-ray structure analysis of 1-(p-tolyl)-4-[4-(N-naphthalimido)butyl]piperazine (I) was carried out: a=9.551(3), b=13.775(3), á=8.917(4) , =103.96(3), =101.47(4), =92.60(3)°, V=1110.4(7) 3, Z=2,calc=1.279 g/cm3, =0.644 mm, space group P 1, 4239 nonzero reflections, R=0.056. The molecule is linear elongated. The p-tolyl and naphthalimide fragments are almost planar, while the piperazine cycle has a chair conformation. The long well-packed molecules form parallel and antiparallel chains with van der Waals interactions between them.  相似文献   

19.
The crystal structure of 1-(2-pyridiniomethyl)-2,4-bis(phenylsulfonyl)benzene bromide, (C24H20NO4S2)+. Br (I) has been investigated by X-ray diffraction (XRD)analysis. The triclinic structure of I (space group P1, a = 7.863 , b = 8.350 , c = 9.043 , = 94.00°, = 97.81°, = 104.62°, Z = 1) was solved by direct methods and refined by full-matrix least-squares analysis in an anisotropic approximation to R = 0.048 for all 4570 reflections collected (CAD-4 automatic diffractometer, CuK ). The geometrical parameters of the organic cation were determined with a sufficient degree of accuracy. The crystal structure of I involves a very strong interionic hydrogen bond N+-HBr.Original Russian Text Copyright © 2004 by A. N. ChekhlovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 759–763, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.  相似文献   

20.
Two heterometallic trinuclear complexes {[Cu(oxbp)]2Co(H2O)2}1.5DMF0.5H2O (complex 1) and {[Cu(oxbm)]2Co(H2O)2}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)] and [Cu(oxbm)][H3oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H3oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm–1 for complex 1 and 2, respectively.  相似文献   

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