首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
The hydrazinium(1+) metal acetates and malonate dihydrates of the molecular formula [(N2H5)2M(CH3COO)4] and (N2H5)2[M(OOCCH2COO)2(H2O)2] respectively, whereM=Co, Ni or Zn, have been prepared and characterized by chemical analyses, conductance, magnetic, spectral, thermal and X-ray powder diffraction studies. The magnetic moments and electronic spectra indicate that these complexes are of high-spin octahedral variety. The infrared spectra show that the hydrazinium ions are coordinated in the case of acetate complexes, whereas in the malonate complexes the hydrazinium ions are out side the coordination sphere. These complexes undergo exothermic decomposition in the temperature range 150–450°C to give the respective metal oxide as the final residue. The X-ray powder diffraction patterns of the malonate complexes indicate isomorphism among them.  相似文献   

2.
Some bis-hydrazine metal pyruvates of transition metal ions of the formula M[CH3COCOO]2 [N2H4]2, where M = Co, Ni, Zn or Cd, tris-hydrazine metal pyruvates of the formula M[CH3COCOO]2 [N2H4]3, where M = Co, Ni, Zn or Cd, and hydrazinium metal pyruvates [N2H5]2M[CH3COCOO]4, where M = Co or Ni have been prepared and the compositions of the complexes have been determined by chemical analysis. The magnetic moments and electronic spectra of the complexes suggest a high-spin octahedral geometry for them. Infrared spectral data of bis-hydrazine complexes indicate the bidentate bridging mode shown by hydrazine molecules and mono dentate coordination by pyruvate ions. However, in tris-hydrazine complexes the pyruvate ions are ionic in nature. In hydrazinium complexes two hydrazinium ions and four pyruvate ions show unidentate coordination mode resulting in six coordination around metal ions. Thermo gravimetry and differential thermal analysis in air reveal that most of the complexes decompose in one step to give the respective metal carbonate as the final residue. However, the hydrazinium complexes yield Co2O3 or NiO as the residue. The final residues were identified by their X-ray powder data. The X-ray powder diffraction patterns of each series of complexes reveal isomorphism among the series.  相似文献   

3.
Alkaline earth metal (Mg, Ca, Sr and Ba) complexes of hippuric acid (hipH) have been synthesized and characterized by elemental analyses and IR spectroscopy. One of the complexes, [Ca(hip)2(H2O)2]·H2O, was characterized by single crystal X-ray diffraction studies. The polymeric structure is based on a dimeric unit and each calcium is coordinated to four hippurate anions and two coordinated water molecules. The hippurate anion functions as a bidentate ligand through the oxygen atoms of the carboxylate groups, one of which is bridging, forming a two dimensional coordination polymer. The water coordination is further confirmed by thermal analysis. The non-linear optical activity of the complexes was also measured.  相似文献   

4.
This paper reports the synthesis and X-ray characteristics of the missing homonuclear s-block metal complex {[Sr2(1,3-pdta)(H2O)6]·H2O}n. In the title compound, the hexadentate 1,3-propanediaminetetraacetate (1,3-pdta) ligand joins to two Sr(II) centers via the diamine chain. Moreover, each Sr(II) is bridged through two carboxylate O atoms and a water molecule to two neighboring Sr(II) ions. The coordination sphere around each Sr(II) ion consists of one diamine nitrogen, four carboxylate oxygens and four water molecules. Comparison with the previously reported M(II)-1,3-pdta complexes reveals that increasing of the ion size results in the incorporation of water molecules into its first coordination sphere and consequent increase of the coordination number (C.N.) from six to seven or eight, while keeping the hexadentate coordination mode of the ligand. Further increase of the metal ion size leads to the loss of the chelating properties of the diamine and formation of a bis-tridentate complex. Associated with it is the change in the binding mode of the carboxylate groups. This forms the basis for classification of divalent metal 1,3-pdta complexes into five distinct structural classes. Additionally, in the present study X-ray powder diffraction and IR spectroscopy were used to distinguish the different structural types of M(II)-1,3-pdta complexes, including Ba[Ba(1,3-pdta)]·2H2O which has been used for their preparation.  相似文献   

5.
The complexes of sulfasalazine (H3Suz) with some of alkaline metals Mg(II), Ca(II), Sr(II) and Ba(II) have been investigated. Sulfasalazine complexes were synthesized and characterized by spectroscopic tools; infrared spectra, electronic and mass spectra. The IR spectra of the prepared complexes were suggested that the H3Suz behaves as a bi-dentate ligand through the carboxylic and phenolic groups. The molar conductance measurements gave an idea about the non-electrolytic behavior of the H3Suz complexes. The thermal decomposition processes for metal(II) complexes of H3Suz viz: [M(HSuz)(H2O)4] (where M = Mg(II), Ca(II), Sr(II) or Ba(II)) have been accomplished on the basis of TG/DTG and DTA studies, and the formula conforms to the stoichiometry of the complexes based on elemental analysis. The kinetic analyses of the thermal decomposition were studied using the Coats–Redfern and Horowitz–Metzger equations. The antitumor and antimicrobial activities of the H3Suz and their alkaline metal(II) complexes were evaluated.  相似文献   

6.
A macrocyclic oxime ligand H6L, which has an O6 cavity surrounded by three N2O2 chelate sites, was synthesized and the multistep oligometal complexation behavior was investigated. Upon complexation with zinc(II), the H6L ligand afforded two kinds of hexanuclear complexes, L2Zn6 then LZn6. Each of the complexation steps proceeded highly efficiently. In the latter complex, a Zn33‐OH) unit was incorporated into the trimetalated ligand, LZn3. The integrated N2O2 chelate coordination sites provide a unique environment for a homometallic complex. The different nature of the peripheral N2O2 sites and the central O6 site is particularly suitable for the selective formation of heterometallic complexes. Complexation with the zinc(II) ion in the presence of alkaline earth (Ca and Ba) or rare earth (La, Eu, Lu) metal ions afforded the heterotetranuclear complexes LZn3M (M=Ca, Ba, La, Eu, Lu), in which zinc(II) and ion M occupied the N2O2 and O6 sites, respectively. Titration experiments showed that the heterometallic complexes LZn3Ca and LZn3Ba were converted into the homometallic complex LZn6 whereas LZn3La was not. As a result, the binding affinity in the central O6 site of the LZn3 unit is apparently in the order of Ca2+, Ba2+3(μ3‐OH)3+. This difference in the affinities of metal ions as well as the ionic sizes makes the novel conversion efficient, particularly in the case of the three‐step conversion from H6L to H2LZn2Ba, LZn3Ba, then LZn6.  相似文献   

7.
The structures of seven divalent metal cation compounds of Ponceau Xylidine {PX; systematic name of dication: 4‐[2‐(3,4‐dimethylphenyl)hydrazin‐1‐ylidene]‐3‐oxo‐3,4‐dihydronaphthalene‐2,7‐disulfonate}, also known as Acid Red 26, CI 16150, and of five divalent metal cation compounds of Crystal Scarlet {CS; systematic name of dication: 8‐[2‐(naphthalen‐1‐yl)hydrazin‐1‐ylidene]‐7‐oxo‐7,8‐dihydronaphthalene‐1,3‐disulfonate}, also known as Acid Red 44, CI 16250, are presented. These are hexaaquamagnesium(II) PX dimethylformamide (DMF) monosolvate, [Mg(H2O)6](C18H14N2O7S2)·C3H7NO, (I); heptaaquacalcium(II) PX 2.5‐hydrate, [Ca(H2O)7](C18H14N2O7S2)·2.5H2O, (II); catena‐poly[aqua(μ‐DMF)tris(DMF)bis(μ3‐PX)distrontium(II)], [Sr(C18H14N2O7S2)(C3H7NO)2(H2O)0.5]n, (III); the transition‐metal series hexaaquametal(II) PX DMF monosolvate, [M(H2O)6](C18H14N2O7S2)·C3H7NO, where M (metal) = Co, (IV), Ni, (V), Cu, (VI), and Zn, (VII); heptaaquacalcium(II) CS monohydrate, [Ca(H2O)7](C20H13N2O7S2)·H2O, (VIII); octaaquastrontium(II) CS monohydrate, [Sr(H2O)8](C20H13N2O7S2)·H2O, (IX); catena‐poly[[triaqua(DMF)barium(II)]‐μ‐CS], [Ba(C20H13N2O7S2)(C3H7NO)(H2O)3]n, (X); tetrakis(DMF)(CS)copper(II) monohydrate, [Cu(C20H13N2O7S2)(C3H7NO)4]·H2O, (XI); and catena‐poly[[[aquatris(DMF)zinc(III)]‐μ‐CS] diethyl ether hemisolvate], {[Zn(C20H13N2O7S2)(C3H7NO)3(H2O)]·0.5C4H10O}n, (XII). In all cases, the structures obtained were solvates with dimethylformamide (DMF) and/or water present. The disulfonated naphthalene‐based azo anions adopt hydrazone tautomeric forms. The structures of the Mg salt and of four transition‐metal forms (M = Co, Ni, Cu and Zn) of PX are found to form an isostructural series. All have solvent‐separated ion‐pair (SSIP) type structures and the formula [M(H2O)6][PX]·DMF. The Ca salt of PX also has an SSIP structure, but has a higher hydration state, [Ca(H2O)7][PX]·2.5H2O. In contrast, the Sr salt of PX, [Sr(PX)(DMF)2(H2O)0.5]n forms a one‐dimensional coordination polymer. Both the Ca and the Sr salt of CS have an SSIP structure, namely [Ca(H2O)7][CS]·H2O and [Sr(H2O)8][CS]·H2O, whilst the heavier Ba analogue, [Ba(CS)(DMF)(H2O)3]n, forms a one‐dimensional coordination polymer. Unlike PX, two CS structures containing transition metals are found to be coordination complexes, [Cu(CS)(DMF)4]·H2O and {[Zn(CS)(DMF)3(H2O)]·0.5Et2O}n. This suggests that CS is a better ligand than PX for transition metals. The Cu complex forms discrete molecules with Cu in a square‐pyramidal environment, whilst the Zn species is a one‐dimensional coordination polymer based on octahedral Zn centres.  相似文献   

8.
The 2014 synthesis of the remarkable dimagnesium compound Mg2[C4(CH3)2(Si(CH3)3)2](C3H7)2(C4H8O)2 may point the way to a new chapter in alkaline earth organometallic chemistry. Accordingly, we have studied the known Mg compound and the analogous Be, Ca, Sr, and Ba structures. Although most of our theoretical predictions come from density functional methods, the latter have been benchmarked using coupled cluster theory including single, double, and perturbative triplet excitations, CCSD(T) using cc‐pVTZ basis sets. Among our most important predictions are the energies for dissociation to the butadiene plus the RM?MR [R=(C3H7)2(C4H8O)2; M=Be, Mg, Ca, Si, and Ba] entities. The most reliable predictions for the dissociation energies are 99–104 (Be), 85–93 (Mg), 90–99 (Ca), 83–92 (Sr), and 83–94 (Ba) kcal mol?1. Thus, there is reason to anticipate that the four unknown compounds should be achievable synthetically. The predicted metal–metal distances (not single bonds) are 2.89 Å (Mg???Mg), 3.46 Å (Ca???Ca), 3.75 Å (Sr???Sr), and 4.04 Å (Ba???Ba). The separated RM?MR compounds have longer M?M distances but genuine metal–metal single bonds. This perhaps counter intuitive result is due to the presence of the bridging carbons in the alkaline earth butadiene compounds. All five compounds incorporate metal–carbon ionic interactions.  相似文献   

9.
The Cluster Azides M2[Nb6Cl12(N3)6]·(H2O)4—x (M = Ca, Sr, Ba) The isotypic cluster compounds M2[Nb6Cl12(N3)6] · (H2O)4—x (M = Ca (1) , M = Sr (2) and M = Ba (3) ) have been synthesized by the reaction of an aequeous solution of Nb6Cl14 with M(N3)2. 1 , 2 and 3 crystallize in the space group Fd3¯ (No. 227) with the lattice constants a = 1990.03(23), 2015.60(12) and 2043, 64(11) pm, respectively. All compounds contain isolated 16e clusters whose terminal positions are all occupied by orientationally disordered azide ligands.  相似文献   

10.
Summary 2-Thenoyltrifluoroacetone isonicotinoyl hydra/one (H2L), made by condensation of 2-thenoyltrifluoroacetone(TTA) with isonicotinic acid hydrazide, and its transition metal complexes were prepared. H2L functions as a tetradentate ligand for divalent metal ions, but as a tridentate ligand for trivalent metal ions, taking part in coordination in both mono- and divalent anions. Antioxidative tests were made to examine the elimination action for H2L and the complexes towards superoxide O inf2 sup–. and hydroxyl OH. radicals, which confirmed the efficient antioxidative action towards these radicals.  相似文献   

11.
Hydrazinium oxydiacetate salts of formulae N2H5(Hoda)⋅H2oda, N2H5(Hoda) and (N2H5)2oda (H2oda=oxydiacetic acid) and complexes of the types, M(oda)⋅2N2H4xH2O (where M=Co, Ni and Cd; x=0 for Co and Ni;x=1 for Cd) and Zn(oda)⋅N2H4⋅H2O have been prepared and characterized by analytical, spectral, thermal and X-ray powder diffraction data. IR data document the existence of N2H+ 5 ion in the simple salts and the bidentate coordination of both hydrazine and dianion in the complexes. Complete decomposition of hydrazinium salts takes place via oxydiacetic acid intermediate. Cobalt and nickel complexes decompose in a single step, whereas zinc and cadmium complexes decompose through hydrazinate intermediates. However, all the metal complexes yield metal oxide as the final residue. Isomorphic nature of the cobalt and nickel complexes is evident from XRD data. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

12.
The structures of the Mg, Ca, Sr and Ba salts of 1‐naphthoic acid are examined and compared with analogous structures of salts of benzoate derivatives. It is shown that catena‐poly[[[diaquabis(1‐naphthoato‐κO)magnesium(II)]‐μ‐aqua] dihydrate], {[Mg(C11H7O2)2(H2O)3]·2H2O}n, exists as a one‐dimensional coordination polymer that propagates only through Mg—OH2—Mg interactions along the crystallographic b direction. In contrast with related benzoate salts, the naphthalene systems are large enough to prevent inorganic chain‐to‐chain interactions, and thus species with inorganic channels rather than layers are formed. The Ca, Sr and Ba salts all have metal centres that lie on a twofold axis (Z′ = ) and all have the common name catena‐poly[[diaquametal(II)]‐bis(μ‐1‐naphthoato)‐κ3O,O′:O3O:O,O′], [M(C11H7O2)2(H2O)2]n, where M = Ca, Sr or Ba. The Ca and Sr salts are essentially isostructural, and all three species form one‐dimensional coordination polymers through a carboxylate group that forms three M—O bonds. The polymeric chains propagate via c‐glide planes and through MOMO four‐membered rings. Again, inorganic channel structures are formed rather than layered structures, and the three structures are similar to those found for Ca and Sr salicylates and other substituted benzoates.  相似文献   

13.
The structures of the hexafluoridoiridates(IV) of calcium, Ca[IrF6]·2H2O [calcium hexafluoridoiridate(IV) dihydrate], strontium, Sr[IrF6]·2H2O [strontium hexafluoridoiridate(IV) dihydrate], and barium, Ba[IrF6] [barium hexafluoridoiridate(IV)], have been determined by single‐crystal X‐ray analysis. The first two compounds are isomorphous. Their metal cations are eight‐coordinated in a distorted square‐antiprismatic coordination environment, and their anions are represented by an almost ideal octahedron. These two structures can be described as frameworks in which all atoms occupy general positions. Sr[RhF6] and Ba[RhF6] have a different space group (, from powder diffraction data) but similar cell dimensions. The structures are very close to that of Ba[IrF6]. The cation is in a cuboctahedral coordination. The metal atoms are located on special positions of symmetry, while the F atoms are in general positions.  相似文献   

14.
Mononuclear Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), Pt(IV), Au(III), and Pd(II) complexes of the drug amlodipine besylate (HL) have been synthesized and characterized by elemental analysis, spectroscopic technique (IR, UV–Vis, solid reflectance, scanning electron microscopy, X-ray powder diffraction, and 1H-NMR) and magnetic measurements. The elemental analyses of the complexes are confirmed by the stoichiometry of the types [M(HL)(X)2(H2O)]·nH2O [M = Mn(II), Co(II), Zn(II), Ni(II), Mg(II), Sr(II), Ba(II), and Ca(II); X = Cl? or NO3 ?], [Cd(HL)(H2O)]Cl2, [Pd(HL)2]Cl2, [Pt(L)2]Cl2, and [Au(L)2]Cl, respectively. Infrared data revealed that the amlodipine besylate drug ligand chelated as monobasic tridentate through NH2, oxygen (ether), and OH of besylate groups in Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), and Au(III) complexes, but in Pt(IV) and Pd(II) complexes, the amlodipine besylate coordinates via NH2 and OH (besylate) groups. An octahedral geometry is proposed for all complexes except for the Cd(II), Pt(IV), and Pd(II) complexes. The amlodipine besylate free ligand and the transition and non-transition complexes showed antibacterial activity towards some Gram-positive and Gram-negative bacteria and the fungi (Aspergillus flavus and Candida albicans).  相似文献   

15.
Some new hydrazinium transition metal sulfite dihydrate complexes of the formula (N2H5)2M(SO3)2(H2O)2 where M=Fe, Co, Ni, Cu and Zn have been prepared and characterized by hydrazine and metal analyses, magnetic studies, electronic and infrared spectra and thermal analysis. The magnetic studies coupled with electronic spectra of iron, cobalt, nickel and copper complexes indicate their high spin octahedral nature. However the zinc complex is diamagnetic and show only the charge transfer transition. The infrared spectra shows that both the hydrazinium ions are coordinated to the metal ions, the sulfite ions are present as bidentate ligand. The simultaneous TG-DTA of these complexes were investigated in air and nitrogen atmospheres. In air, cobalt, nickel and zinc complexes give respective metal sulfate as the final residue while iron and copper complexes give the mixture of respective metal oxide and sulfate as the decomposition product. In nitrogen atmosphere respective metal sulfites are formed as the end residue.  相似文献   

16.
Summary High-yield synthetic routes to trinuclear complexes of the type [M(OsA3)2] (M = Mg, Ca, Sr or Ba; A = anion of arylazo oxime) by reaction of Na[OsA3] and M(ClO4)2, or of [HOsA3] with MCO3, are described. The new complexes have been characterized on the basis of spectroscopic and physico-chemical results. The alkaline earth metal ions are held in an O6 matrix of two facial [OsA3] units, each behaving as a tridentate (O, O, O) ligand. Quantitative transport of one equivalent of M2+ from the aqueous to the organic (CH2Cl2) phase can be achieved with two equivalents of [OsA3]. When the aqueous phase is acidified with two mol of H+, [M(OsA3)2] decomposes into M2+ and [HOsA3], and M2+ returns to this phase in its free state.  相似文献   

17.
The thermal dissociation of the cupferron complexes with Cu(II), Ni, Co(II), Zn, Cd, Mn(II), Hg(II), Mg, Ca, Ba, Sr, Al, Fe(III). Ce(III), La, and Nd was studied by differential thermal analysis (DTA) and by pyrolysis into a mass spectrometer. The DTA curves consisted mainly of endothermic peaks although some contained exothermic peaks as well. The mass spectrometer showed that cupferron decomposes slightly above room temperature, giving off N2, NO, N2O, NH3 and H2O. A mechanism for the thermal dissociation of the coppcr(II) cupferrate is proposed.  相似文献   

18.
Lighter and heavier lanthanide(III) ions react with dihydrazinium salts of ethylenediaminetetraacetic acid (H4edta) in aqueous solution to yield hydrazinium lanthanide ethylenediaminetetraacetate hydrate, N2H5[Ln(edta)(H2O)3]·(H2O)5 where Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy. The numbers of water molecules present inside the coordination sphere have been confirmed by X-ray single crystal studies. The presence of five water molecules as lattice water is clearly shown by the mass loss from the TG analyses. Dehydration of a known amount (1 g) of each sample were carried out at constant temperature (100–110°C) for about 5 min further confirms the number of non-coordinated water molecules. The complexes after the removal of lattice water undergo multi-step decomposition to give respective metal oxide as the final product. The DTA shows endotherms for dehydration and exotherms for the decomposition of the anhydrous complexes. The formation of the metal oxides was confirmed by X-ray powder diffraction studies.  相似文献   

19.
The hydroxide, oxalate and citrate precursors of the metal oxides such as γ-Fe2O3, (MnZn)Fe2O4, Cu(K)Fe2O4, BaTiO3, La(Sr)MnO3, La(Sr)AlO3, La/Gd(Ca/Ba/Sr)CoO3, and anatase TiO2 on modifications with the hydrazine decompose at low temperatures give single phase oxides of superior properties, while the complexes without such modification require higher temperatures for achieving the phases. The hydrazine released at lower temperatures reacts with the oxygen in the atmosphere, N2H4+O2→N2+2H2O; ΔH=−625 kJ mol−1, and liberates enormous energy that is sufficient for the oxidative decomposition of the complexes now devoid of hydrazine. Such extra energy is not available in the case of the precursors without such modifications. The reaction products of hydrazine oxidation provide desired partial pressure of moisture needed for the stabilization of γ-Fe2O3. Also, the nitrogen that is formed in the reaction of hydrazine with oxygen gets trapped in the lattice of TiO2 giving yellow color nitrogen doped TiO2−xNx photocatalyst. Thus, hydrazine method of preparation has many advantages in the preparation of metal oxides of superior properties.  相似文献   

20.
Hydrazinium metal ethylenediaminetetraacetate complexes of molecular formula (N2H5)2[Mg(edta)·H2O], (N2H5)3[Mn(edta)··H2O](NO3)·H2O, N2H5[Fe(edta)·H2O], N2H5[Cu(Hedta)·H2O] and N2H5[Cd(Hedta)·H2O]·H2O have been synthesized and characterized by elemental and chemical analysis, conductivity and magnetic measurements and spectroscopic techniques. The thermal behaviour of these complexes has been studied by thermogravimetry and differential thermal analysis. The data set provided by the simultaneous TG-DTA curves of the complexes shows the occurrence of three or four consecutive steps such as dehydration, ligand pyrolysis and formation of metal oxides. X-ray powder diffraction patterns of copper and cadmium complexes show that they are not isomorphous. These studies suggest seven coordination for Mg,Mn, Fe complexes and six coordination for Cu and Cd derivatives.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号