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1.
Summary Reactions of glyoxal bis(morpholineN-thiohydrazone), H2gbmth, with NiCl2·6H2O, Ni(OAc)2·4H2O, Ni(acac)2· H2O, CuCl2·2H2O, Cu(OAc)2·H2O, Cu(acac)2, CoCl2· 6H2O, Co(OAc)2·4H2O and Co(acac)2·2H2O yield complexes of the type [M(gbmth)], [M=NiII, CuII or CoII]. Diacetyl reacts with morpholineN-thiohydrazide in the presence of nickel salts to yield [NiII(dbmth)], [NiII(dmth)(OAc)]H2O and [NiII(Hdmth)(NH3)Cl2] involving N2S2 and NSO donor ligands. Copper and cobalt complexes of N2S2 and NSO donor ligands with compositions [CuII(dbmth)], [CoII(dbmth)]·4H2O and [CoII(H2dbmth)]Cl2, have been isolated. The compounds have been characterised by elemental analyses, magnetic moments, molar conductance values and spectroscopic (electronic and infrared) data.  相似文献   

2.
Summary Cobalt(II) and nickel(II) complexes of 4-amino-6-methyl-5-oxo-3-phenylamino-1,2,4-triazine (ATAZ), MX2(ATAZ)2 · 2 H2O (M = Co or Ni; X = Cl, Br, I or NCS), have been isolated. The electronic spectra, magnetic moments and i.r. spectra of the compounds have been studied.Pseudo-octahedral environments are proposed for the complexes: [MX2(ATAZ)2]. 2 H2O (M = Ni or Co; X = Cl or Br) and [CoI2(ATAZ)2(H2O)2], and apseudo-tetrahedral structure for [NiX2(ATAZ)2] · 2 H2O (X = I or NCS) and [Co(NCS)2-(ATAZ)2] · 2 H,O. However, [CoX2(ATAZ)2]. 2 H2O (X = Cl or Br) give acetone solutions containing tetrahedral cobalt(II).  相似文献   

3.
Summary Complexes of formula [MCl3(glyH)3] (M=Ti, V and Fe) [CrCl3(glyH)2H2O], [MCl2(glyH)2(H2O)2] (M=Co and Cu) and [NiCl2(glyH)3H2O] have been prepared and characterized by potentiometric curves, chemical analysis, magnetic properties, i.r. and electronic spectral data.  相似文献   

4.
New complexes of the formulae K3[RhL 3]·2 H2O, [PdL]·H2O and [M(LH2)Cl2] [whereM = Pd, Pt andLH2 = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and1H-NMR spectroscopy.
Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)
Zusammenfassung Neue Komplexe der allgemeinen Formeln K3[RhL 3]·2H2O, [PdL]·H2O und [M(LH2)Cl2] mitM = Pd, Pt undLH2 = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und1H-NMR-Spektroskopie charakterisiert.
  相似文献   

5.
Summary The new complexes K2[Ni(H2heo)2]·3H2O, K2[Pd-(H2heo)2], K2[Cu(heo)]·3H2O and [Cu2(heo)·2H2O] {heo = [(CONCH2CH2O)2]4-} were prepared and characterized by chemical analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and i.r. and u.v. spectroscopy.Monomeric square planar structures with MN4 coordination spheres are found for the nickel and palladium complex anions.For copper, two different complexes were identified. In slightly alkaline media, a green insoluble nonelectrolyte [Cu2(heo)·2H2O] was prepared; the two copper(II) centres are bridged by the tetra-deprotonated ligand in a trans-planar configuration with the H2O molecules strongly coordinated to the copper(II). The copper(II) monomer has been prepared in strong alkaline media, this anion also contains the tetra-deprotonated ligand in a planar trans form.  相似文献   

6.
Summary The following coordination compounds derived from 2-guanidinobenzimidazole (2GB) (1); [Ni(2GB)2]Cl2· H2O, (2); [Ni(2GB)2]Br2·3H2O, (3); [Ni(2GB)2-(NO3)2, (4); [Ni(2GB)2](OAc)2, (5); [Cu(2GB)Cl2], (6); [Cu(2GB)Br2], (7); [Cu(2GB)2]Br2·2H2O, (8); [Cu(2GB)2](NO3)2·H2O, (9); [Cu(2GB)2](OAc)2· H2O, (10); [Zn(2GB)Cl2]·H2O, (11); [Zn(2GB)Br2]·H2O, (12); [Co(2GB)Cl2(H2O)2]·5H2O, (13); [Co-(2GB)2Cl2]·3H2O, (14); [Co(2GB)2(H2O)2](NO3)2· 4H2O, (15); and [Co(2GB)2(H2O)2](OAc)2, (16) have been synthesized and characterized by i.r. and electronic spectroscopy. In addition (6)–(10) were analysed by e.p.r. The X-ray diffraction structure of compound (4) was obtained. It crystallizes in the monoclinic system, C2/c (a = 22.511(7), b = 6.735(6) and c= 15.345(5)Å, =115.31(3)°, Z = 4, final R = 0.0360 and R w = 0.0388 for 1167 observed independent reflections). The nickel(II) atom coordinates two ligands in a square-planar geometry through the imidazolic N(3) and the guanidino N(12).The probable ligand isomers involved in the coordination were determined by theoretical calculations, and the possible structures of the coordination compounds were investigated in order to verify that the experimentally proposed structures were stable. Two different types of coordination compounds were found. One, where the ligand is chelating through the imidazolic N(3) and the guanidino N(12), which is the case for most of the complexes [(2)–(13)]. With only one ligand in the coordination sphere, the structure was either tetrahedral (copper and zinc chloride and bromide complexes) or octahedral (cobalt). With two chelating 2GB units a square-planar geometry was stabilized [(2)–(5) and (8)–(10)]. The second type of coordination behaviour was observed in the cobalt compounds [(14)–(16)]. Here the ligand coordinates monodentate through the imidazolic N(3); the structure is tetrahedral.  相似文献   

7.
Summary N-Cyano-N-methyl-N(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with CoII, NiII and CuII are described. The compounds are of stoichiometry [M(CM)2]SO4 · nH2O [M = CoII, NiII or CuII; n = 3,3 or 4, respectively], [M(CM)2](ClO4)2 [M = CoII or NiII], [M(CM)2]Cl2 · nH2O [M=CoII, NiII or CuII; n = 1, 2, or 2, respectively] and [Cu(CM)SO4] · 2H2O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM)2]SO4·nH2O, [M(CM)2](ClO4)2, [Ni(CM)2]Cl2 · 2H2O, [Cu(CM)2]Cl2 · 2H2O and [Cu(CM)SO4] · 2H2O and a tetrahedral structure for [Co(CM)2]Cl2 · H2O.  相似文献   

8.
An interesting series of nine new copper(II) complexes [Cu2L2(OAc)2]·H2O (1), [CuLNCS]·½H2O (2), [CuLNO3]·½H2O (3), [Cu(HL)Cl2]·H2O (4), [Cu2(HL)2(SO4)2]·4H2O (5), [CuLClO4]·½H2O (6), [CuLBr]·2H2O (7), [CuL2]·H2O (8) and [CuLN3]·CH3OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the dx2-y2 orbital. The structure of the compound, [Cu2L2(OAc)2] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P21/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.  相似文献   

9.
Nickel(II) complexes with 6-benzylaminopurine (BAP) derivatives, namely 6-(3-chlorobenzylamino)purine (HL1), 6-(4-chlorobenzylamino)purine (HL2) and 6-(4-fluorobenzylamino)purine (HL3), have been prepared and characterized by elemental analyses, i.r., u.v.–v.i.s., ES+ and FAB+ mass spectroscopy, magnetic susceptibility and conductivity measurements, and by thermal analysis. The complexes are: [Ni(L1(H2O)2Cl] · H2O, [Ni(L1)(H2O)-(NO3)] · H2O, [Ni(L2)(H2O)2Cl], [Ni(L2)(H2O)2(NO3)] · H2O, [Ni(HL2)(H2O)Cl2] · EtOH and [Ni(L3)(H2O)2Cl]. They have been tested in vitro for their possible cytotoxic activity against G-361 (human malignant melanoma), HOS (human osteogenic sarcoma), K-562 (human chronic myelogenous leukemia) and MCF-7 (human breast adenocarcinoma) cell lines.  相似文献   

10.
The new orotic acid complexes, [MCl2(H2O)3(H3Or)], M=Co(II), Ni(II) and [CuCl2(H2O)(H3Or)3] · H2O, were synthesized and characterized by elemental analysis, magnetic susceptibility, spectral (Diffuse reflectance UV–Vis and FTIR) methods, and simultaneous thermal analysis (TG, DTG and DTA) techniques. Physical measurements indicate that the neutral orotic acid ligands are bonded to metal ions through the carbonyl groups. Two thermal processes of the complexes can occur: dehydration and pyrolytic decomposition. On the basis of the DTGmax, the thermal stability of the complexes follows the order: Co(II) (122 °C) > Cu(II) (77 °C) > Ni(II) (66 °C).  相似文献   

11.
The reaction of CuSO4 · H2O with 4-bpytm [4-bpytm = bis(4-pyridylthio)methane] in EtOH afforded the complex [Cu(SO4)(4-bpytm)(H2O)3] · H2O (1 · H2O) while the reaction of 4-bpytm with Cu(NO3)2 · 3H2O in EtOH afforded the complex [Cu(NO3)2(4-bpytm)2] · H2O (2 · H2O). The reaction of 4-bpytm with Cu(NO3)2 · 3H2O in EtOH/dmf under microwave irradiation afforded the pseudo-polymorph [Cu(NO3)2(4-bpytm)2] · Solv (2 · Solv). Compound 1 · H2O forms helical chains while compounds 2 · H2O and 2 · Solv are 2D coordination polymers with a (4,4) topology based on rhombic grids in 2 · H2O and on a parquet motif in 2 · Solv. The 3D supramolecular organization through hydrogen bonding is analyzed for the three compounds and their thermal behaviour was also investigated.  相似文献   

12.
Chiral and racemic Salen-type Schiff-base ligands (H2L1, H2L2 and H2L3), condensed between D-(+)- and D,L-camphoric diamine (also known as (1R,3S)-1,2,2-trimethylcyclopentane-1,3-diamine) and 2-hydroxybenzaldehyde or 3,5-dibromo-2-hydroxybenzaldehyde with a 1:2 molar ratio, have been synthesized and characterized. A series of new nickel(II), palladium(II) and copper(II) complexes of these chiral and racemic ligands exhibiting different coordination number (4, 5 and 6) have been characterized with the formulae [NiL1]·CH3OH (3), [NiL1]·H2O (4), [NiL2] (5), [PdL2] (6), [Cu2(L2)2(H2O)] (7) and [NiL3(DMF)(H2O)] (8). Different solvent molecules in 3 and 4 (methanol and water molecules) as well as different apical ligands in 7 and 8 (water and DMF molecules) are involved in different O–H···O hydrogen bonding interactions to further stabilize the structures. UV–Vis (UV–Vis), circular dichroism (CD) spectra and thermogravimetric (TG) analyses for the metal complexes have also been carried out.  相似文献   

13.
The formation of magnetically active polynuclear FeIII pivalates in the FeSO4·7H2O-KOOCCMe3 system was studied. The reaction of FeSO4·7H2O (1) with KOOCCMe3 in EtOH in air afforded the antiferromagnetic trinuclear complex [Fe3O(OOCCMe3)6(H2O)3]+[OOCCMe3]·3EtOH. A change of the solvent (EtOH) in this system to a 40:1 benzene—THF mixture resulted in the formation of the antiferromagnetic hexanuclear cluster [Fe6(O)2(OH)2(OOCCMe3)12(HOOCCMe3)(THF)]·1.5C6H6. The addition of trimethylacetic acid to EtOH and recrystallization from hexane gave rise to the antiferromagnetic coordination polymer [K2Fe4(O)2(OOCCMe3)10(HOOCCMe3)2(H2O)2]n (7). Recrystallization of the latter from acetonitrile afforded the antiferromagnetic tetranuclear complex K2Fe4(O)2(OOCCMe3)10(HOOCCMe3)2(MeCN)2. The structures of these compounds were established by X-ray diffraction analysis, and their magnetic susceptibilities and thermal decomposition were investigated.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2403–2413, November, 2004.  相似文献   

14.
When kept in dilute acetonitrile solutions, complexes [CoB6][Co(CO)4]2 [B = C5H5N, Me2NC(O)H] form gels CoB x (MeCN) y ](OH)2·2[CoCO3·2CoO·2H2O] (x = 2, 3, y = 4, 3), while the polyfunctional complex [Co{(EtO)3SiCH2CH2CH2NH2)}][Co(CO)4]2 gives a mixed carbonate-siloxane gel. The gel formation is accompanied by complete decomposition of [Co(CO)4]- anions under the action of air oxygen and moisture, to give CoCO3·2CoO·2H2O. Mechanistically, the gel and film formation involves absorption of molecular oxygen by the hexamine- or hexamidecobalt(II) cation and subsequent decomposition of theunstable oxygenated carbonylcobalt complex.  相似文献   

15.
Summary The complexes, [NiL2]Br2 (L=2-methyl-1, 2-propanediamine), [NiL2(H2O)2]SeO4·2H2O, [NiL2]X2·2H2O (X=0.5SO4 or 0.5SeO4) and [NiL2(NCS)2] have been prepared and investigated thermally. Upon heating, [NiL2]Br2 exhibits reversible thermochromism from yellow to blue: [NiL2]X2·2H2O (X=0.5SO4 or 0.5SeO4) undergoes dehydration accompanied with irreversible thermochromism from yellow to blue yielding [NiL2X2], whereas [NiL2(H2O)2]SeO4·2H2O (blue) transforms irreversibly into [NiL2SeO4] (blue). [NiL2]X2 (X=0.5SO4 or 0.5SeO4), prepared from their corresponding diaquo complexes by the temperature arrest technique, shows irreversible thermochromism from yellow to blue without showing any peak in the d.t.a./d.s.c. curves. [NiL2(NCS)2] (blue) undergoes a thermally induced phase transition without any visual change. All the yellow species are square planar; the blue species are octahedral. These colour changes are due to configurational changes; the phase change in [NiL2(NCS)2] is probably due to conformational changes in the diamine chelate rings.  相似文献   

16.
The synthesis, reduction, optical and e.p.r. spectral properties of a series of new binuclear copper(II) complexes, containing bridging moieties (OH, MeCO2 , NO2 , and N3 ), with new proline-based binuclear pentadentate Mannich base ligands is described. The ligands are: 2,6-bis[(prolin-1-yl)methyl]4-bromophenol [H3L1], 2,6-bis[(prolin-1-yl)methyl]4-t-butylphenol [H3L2] and 2,6-bis[(prolin-1-yl)methyl]4-methoxyphenol [H3L3]. The exogenous bridging complexes thus prepared were hydroxo: [Cu2L1(OH)(H2O)2] · H2O (1a), [Cu2L2(OH)(H2O)2] · H2O (1b), [Cu2L3(OH)(H2O)2] · H2O (1c), acetato [Cu2L1(OAc)] · H2O (2a), [Cu2L2(OAc)] · H2O (2b), [Cu2L3(OAc)] · H2O (2c), nitrito [Cu2L1(NO2)(H2O)2] · H2O (3a), [Cu2L2(NO2)(H2O)2] · H2O (3b), [Cu2L3(NO2)(H2O)2] · H2O (3c) and azido [Cu2L1(N3)(H2O)2] · H2O (4a), [Cu2L2(N3)(H2O)2] · H2O (4b) and [Cu2L3(N3)(H2O)2] · H2O (4c). The complexes were characterized by elemental analysis and by spectroscopy. They exhibit resolved copper hyperfine e.p.r. spectra at room temperature, indicating the presence of weak antiferromagnetic coupling between the copper atoms. The strength of the antiferromagnetic coupling lies in the order: NO2 N3 OH OAc. Cyclic voltammetry revealed the presence of two redox couples CuIICuII CuIICuI CuICuI. The conproportionality constant K con for the mixed valent CuIICuI species for all the complexes have been determined electrochemically.  相似文献   

17.
The new complexes [Co(ecpzdtc)3] (2) [Zn(ecpzdtc)2(py)] (3) and [Cd(ecpzdtc)2(py)]·H2O (4) have been synthesized from sodium 1-ethoxycarbonyl-piperazine-4-carbodithioate [(Na+(ecpzdtc)]. The ligand and the complexes have been characterized by elemental analyses, IR, magnetic susceptibility and single crystal X-ray data. The [Zn(ecpzdtc)2(py)] and [Cd(ecpzdtc)2(py)]·H2O complexes contain pyridine as the co-ligand. [Co(ecpzdtc)3] (2) crystallizes in the monoclinic system, whereas [Zn(ecpzdtc)2(py)] (3) and [Cd(ecpzdtc)2(py)]·H2O (4) crystallize in the triclinic system. The sulfur donor sites of the bidentate ligand chelate the metal center, forming a four-membered CS2M ring. The cobalt complex has a distorted octahedral geometry, the zinc complex is almost between trigonal bipyramidal and square pyramidal, whereas the cadmium complex is square pyramidal. The crystal structures of all the complexes are stabilized by various types of inter and intramolecular hydrogen bonding.  相似文献   

18.
Summary The reactions of MCl3·3H2O (M=Ru, Rh or Ir) with hydrazones have been studied by three different methods and complexes of the types [M(LH2)(H2O)2]Cl3, [M(L)Cl(H2O)] and [M(LH2)Cl2]Cl·H2O have been isolated. Tentative structural conclusions are drawn for these products based upon elemental analysis, electrical conductance, magnetic moment, and i.r. and1H n.m.r. data. The thermal stability and mode of decomposition for the complexes have been studied by t.g.a., d.t.g. and d.s.c. techniques.  相似文献   

19.
Summary The new complexes K2[ML2]·2H2O (M=Ni, Cu), K2[PdL2]·H2O, K2[CuL2(H2O)2]·H2O, [Ni(LH2)Cl2]x ·xH2O and [Ni(LH2)Br2]x·1,5xH2O, where LH2= oxalyldihydrazide, have been prepared. Emphasis has been put on determining the conditions for the synthesis of both deprotonated and non-deprotonated NiII complexes. They were characterized by analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and spectroscopic methods like i.r. and far-i.r., diffuse reflectance u.v. vis, and e.s.r. Monomeric square planar and distorted octahedral structures were found for the deprotonated complexes in the solid state while the non-deprotonated NiII complexes appeared to be pseudo-tetrahedral polymers. The doubly deprotonated L2-ion exhibits a bidentate N(amide), N(amide)-coordination, while the neutral LH2 molecule behaves as a N(amino), N(amino)-bidentate ligand forming polymeric structures. Vibrational analysis of the complexes was carried out, using hydrogen and metal isotopic substitution.  相似文献   

20.
Summary Thorium acetylacetonate [Th(acac)4] reacts with pyridine carboxylic acids in acetone giving eight coordinate thorum(IV) complexes of the compositions [Th(pic)4] and [Th(picO)4] (picH = picolinic acid, picOH = picolinic acidN-oxide). The complex [Th(dip)2] · 3H2O (dipH2 = pyridine-2,6-dicarboxylic acid) is also reported. Thorium(IV) complexes of the types [Th(quin)2] · 2H2O and [Th(quind)2(acac)2] (quinH2 = quinolinic acid or pyridine-2,3-dicarboxylic acid, quindH = quinaldinic acid) were prepared by the interaction of [Th(acac)4] with the respective acids in acetone. The lower solubility and i.r. spectral studies of the complex [Th(quin)2] · 2 H2O suggest that it is polymeric.  相似文献   

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