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 31 毫秒
1.
The coordination capability of a pendant-arm azamacrocyclic ligand L with four ethyldioxolane pendant groups towards transition, post-transition and lanthanide metal ions was achieved. In all cases, complexes with a 2:1 metal:ligand molar ratio were obtained. The complexes were characterized by elemental analysis, MS-FAB, IR, conductivity measurements, 1H and 13C NMR spectroscopy. Crystal structures of [CoL][CoBr0.5(NO3)3.5] and [(H2O)H2L][Nd(NO3)4(H2O)3]NO3·3.5H2O have been determined. The [CoL]2+ cation contains the Co(II) ion endomacrocyclicly coordinated in a distorted octahedral geometry with a N6 core. The Nd(III) complex presents a mononuclear exomacrocyclic structure with an 11 coordination environment. π,π-Stacking interactions have been observed between the pyridine rings of the protonated ligand [(H2O)H2L]2+, and the [Nd(NO3)4(H2O)3]2− anion.  相似文献   

2.
Five coordination compounds of bismuth, lanthanum and praseodymium nitrate with the oxygen‐coordinating chelate ligand (iPrO)2(O)PCH2P(O)(OiPr)2 (L) are reported: [Bi(NO3)3(L)2] ( 1 ), [La(NO3)3(L)2] ( 2 ), [Pr(NO3)3(L)2] ( 3 ), [La(NO3)3(L)(H2O)] ( 4 ) and [Pr(NO3)3(L)(H2O)] ( 5 ). The compounds were characterized by means of single crystal X‐ray crystallography, 1H and 31P NMR spectroscopy in solution, solid‐state 31P NMR spectroscopy, IR spectroscopy, DTA‐TG measurements ( 1 , 2 and 4 ), conductometry and electrospray ionization mass spectrometry (ESI‐MS). In addition, DFT calculations for model compounds of 1 and 2 support our experimental work. In the solid state mononuclear coordination compounds were observed for 1 — 3 , whereas compounds 4 and 5 gave one‐dimensional hydrogen‐bonded polymers via water‐nitrate coordination. Despite of the similar ionic radii of bismuth(III), lanthanum(III) and praseodymium(III) for a given coordination number the bismuth and lanthanide compounds 1 — 3 are not isostructural. The bismuth compound 1 shows a 9‐coordinate bismuth atom whereas lanthanum(III) and praseodymium(III) atoms are 10‐coordinate in the lanthanide complexes 2 — 5 . The general LnO10 coordination motif in compounds 2 — 5 is best described as a distorted bi‐capped square antiprism. The BiO9 polyhedron might be deduced from the LnO10 polyhedron by replacing one oxygen ligand with a stereochemically active lone pair. The one‐to‐one complexes 4 and 5 dissociate in solution to give the corresponding one‐to‐two complexes 2 and 3 , respectively, and solvated Ln(NO3)3. In contrast to the lanthanides, the one‐to‐two bismuth complex 1 is less stable in CH3CN solution and partially dissociates to give solvated Bi(NO3)3 and (iPrO)2(O)PCH2P(O)(OiPr)2.  相似文献   

3.
Four CuII and CoII complexes–[Cu(L1)Cl2(H2O)]3/2H2O · 1/2EtOH, [Cu(L1)2Cl2]6H2O, [Co(L1)Cl2]3H2O · EtOH, and [Co2(L1)(H2O)Cl4]1.5H2O · EtOH (L1 = 2,4,6-tri(2-pyridyl)-1,3,5-triazine; TPT)–were synthesized by conventional chemical method and used to synthesize another four metal complexes–[Cu(L1)I2(H2O)]6H2O, [Cu(L1)2I2]6H2O, [Co(L1)I(H2O)2]I · 2H2O, and [Co2(L1)I4(H2O)3]–using tribochemical reaction, by grinding it with KI. Substitution of chloride by iodide occurred, but no reduction for CuII or oxidation of CoII. Oxidation of CoII to CoIII complexes was only observed on the dissolution of CoII complexes in d6-DMSO in air while warming. The isolated solid complexes (CuII and CoII) have been characterized by elemental analyses, conductivities, spectral (IR, UV-Vis, 1H-NMR), thermal measurements (TGA), and magnetic measurements. The values of molar conductivities suggest non-electrolytes in DMF. The metal complexes are paramagnetic. IR spectra indicate that TPT is tridentate coordinating via the two pyridyl nitrogens and one triazine nitrogen forming two five-membered rings around the metal in M : L complexes and bidentate via one triazine nitrogen and one pyridyl nitrogen in ML2 complexes. In binuclear complexes, L is tridentate toward one CoII and bidentate toward the second CoII in [Co2(L1)Cl4]2.5H2O · EtOH and [Co2(L1)I4(H2O)3]. Electronic spectra and magnetic measurements suggest a distorted-octahedral around CuII and high-spin octahedral and square-pyramidal geometry around CoII.  相似文献   

4.
Four new complexes [Nd(phen)2(pcyd)3] (1), [Nd(phen)2(2-Clpcyd)3] (2), [Nd(phen)2(2,3,5-Cl3pcyd)3] (3) and [Nd(phen)2(2,3,4,5-Cl4pcyd)3] (4) where pcyd = phenylcyanamide anion, 2-Clpcyd = (2-chlorophenyl)cyanamide anion, 2,3,5- Cl3pcyd = (2,3,5-threechlorophenyl)cyanamide anion and 2,3,4,5-Cl4pcyd = (2,3,4,5-tetrachlorophenyl)cyanamide anion, were prepared and characterized by IR, UV-Vis and 1H NMR spectroscopy as well as elemental analysis. The 1H NMR spectra of these complexes show broadening of ligand protons attributed to coordination of paramagnetic center.  相似文献   

5.
The synthesis, characterization and ε‐caprolactone polymerization behavior of lanthanide amido complexes stabilized by ferrocene‐containing N‐aryloxo functionalized β‐ketoiminate ligand FcCOCH2C(Me)N(2‐HO‐5‐But‐C6H3) (LH2, Fc = ferrocenyl) are described. The lanthanide amido complexes [LLnN(SiMe3)2(THF)]2 [Ln = Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] were synthesized in good yields by the amine elimination reactions of LH2 with Ln[N(SiMe3)2]3(µ‐Cl)Li(THF)3 in a 1:1 molar ratio in THF. These complexes were characterized by IR spectroscopy and elemental analysis, and 1H NMR spectroscopy was added for the analysis of complex 4 . The definitive molecular structures of complexes 1 and 3 were determined by X‐ray diffraction studies. Complexes 1 – 4 can initiate the ring‐opening polymerization of ε‐caprolactone with moderate activity. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

6.
刘强  张帅  杜凯  尹强  李娃  蔡佩君 《无机化学学报》2018,34(6):1143-1148
在温和条件下合成了2种以β-二酮和三苯氧膦为配体的钕三元配合物[Nd(TTA)_3(TPPO)_2](1)(TTA=2-噻吩甲酰三氟丙酮,TPPO=三苯氧膦)和[Nd(BFA)_3(TPPO)_2](2)(BFA=4,4,4-三氟-1-苯基-1,3丁二酮),获得了单晶并通过X射线单晶衍射确定了配合物结构。晶体分析显示,2种配合物均为八配位结构,属于三斜晶系,P1空间群。采用元素分析、红外光谱和热重分析对2种配合物进行了结构表征;通过近红外荧光分析,探讨了配合物的荧光特征。  相似文献   

7.
The reaction of the aryl‐oxide ligand H2L [H2L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO4 · 5H2O, CuCl2 · 2H2O, CuBr2, CdCl2 · 2.5H2O, and Cd(OAc)2 · 2H2O, respectively, under hydrothermal conditions gave the complexes [Cu(H2L1)2] · SO4 · 3CH3OH ( 1 ), [Cu2(H2L2)2Cl4] ( 2 ), [Cu2(H2L2)2Br4] ( 3 ), [Cd2(HL)2Cl2] ( 4 ), and [Cd2(L)2(CH3COOH)2] · H2L ( 5 ), where H2L1 [H2L1 = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H2L2 [H2L2 = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.  相似文献   

8.
Abstract

A new tripodal O-donor ligand, tris(2-N,N-dibutylcarbamoylmethoxyphenyl)phosphine oxide (L), was synthesized. This potentially tetradentate ligand L exhibits variable denticity upon complexation with UO2(NO3)2, Nd(NO3)3, and Lu(NO3)3. The complexes were studied by elemental analysis, IR, and 1H, 13C, and 31P NMR spectroscopy.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, tables, and figures.]  相似文献   

9.
The interaction of lanthanide(III) ions with two N3O3-macrocycles, L1 and L2, derived from 2,6-bis(2-formylphenoxymethyl)pyridine and 1,2-diaminoethane has been investigated. Schiff-base macrocyclic lanthanide(III) complexes LnL1(NO3)3 · xH2O (Ln = Nd, Sm, Eu or Lu) have been prepared by direct reaction of L1 and the appropriate hydrated lanthanide nitrate. The direct reaction between the diamine macrocycle L2 and the hydrated lanthanide(III) nitrates yields complexes LnL2(NO3)3· H2O only for Ln = Dy or Lu. The reduction of the Schiff-base macrocycle decreases the complexation capacity of the ligand towards the Ln(III) ions. The complexes have been characterised by elemental analysis, molar conductivity data, FAB mass spectrometry, IR and, in the case of the lutetium complexes, 1H NMR spectroscopy.  相似文献   

10.
Treatment of Ln(NO3)3?nH2O with 1 or 2 equiv 2,2′‐bipyrimidine (BPM) in dry THF readily afforded the monometallic complexes [Ln(NO3)3(bpm)2] (Ln=Eu, Gd, Dy, Tm) or [Ln(NO3)3(bpm)2]?THF (Ln=Eu, Tb, Er, Yb) after recrystallization from MeOH or THF, respectively. Reactions with nitrate salts of the larger lanthanide ions (Ln=Ce, Nd, Sm) yielded one of two distinct monometallic complexes, depending on the recrystallization solvent: [Ln(NO3)3(bpm)2]?THF (Ln=Nd, Sm) from THF, or [Ln(NO3)3(bpm)(MeOH)2]?MeOH (Ln=Ce, Nd, Sm) from MeOH. Treatment of UO2(NO3)2?6H2O with 1 equiv BPM in THF afforded the monoadduct [UO2(NO3)2(bpm)] after recrystallization from MeOH. The complexes were characterized by their crystal structure. Solid‐state luminescence measurements on these monometallic complexes showed that BPM is an efficient sensitizer of the luminescence of both the lanthanide and the uranyl ions emitting visible light, as well as of the YbIII ion emitting in the near‐IR. For Tb, Dy, Eu, and Yb complexes, energy transfer was quite efficient, resulting in quantum yields of 80.0, 5.1, 70.0, and 0.8 %, respectively. All these complexes in the solid state were stable in air.  相似文献   

11.
Reaction of [Ru(Me2SO)3(O2CCF3)2(H2O)] with triphenylphosphine and triphenylarsine gives complexes of the type [Ru(Me2SO)(O2CCF3)2(EPh3)2] (where E?=?P or As) in which there is a partial substitution of dimethylsulfoxide. Reaction with unidentate N donors resulted in [Ru(O2CCF3)2L4] (where L?=?pyridine, imidazole, benzimidazole); reaction with diimines yielded [Ru(L–L)3](O2CCF3)2 (where L–L?=?2,2′-bipyridyl, 1,10-phenanthroline). All complexes have been characterized by elemental analysis, conductivity measurements, IR and 1H NMR spectroscopy.  相似文献   

12.
(E)-2-(2-hydroxybenzylideneamino)isoindoline-1,3-dione (Hbid) was prepared by condensation of N-aminophthalimide and salicylaldehyde and characterized by elemental analysis, IR, 1H-NMR, and mass spectral studies. Mononuclear complexes [(phen)CuII(μ-Hbid)2H2O] (1), [(phen)CoII(Cl)2(μ-Hbid)]6H2O (2) (phen?=?1,10-phenanthroline) and binuclear complexes [CuII(μ-Hbid)]2 (3), and [CoII(μ-Hbid)]2 (4) with Hbid were prepared and characterized by elemental analysis, IR, UV-Vis, molar conductance, and thermogravimetric (TG) techniques. DNA-binding properties of 14 were investigated by UV spectroscopy, fluorescence spectroscopy, and viscosity measurements. The results suggest that 1 and 2 bind to DNA by partial intercalation, whereas 3 and 4 find different groove-binding sites. The cleavage of these complexes with super coiled pUC19 has been studied using gel electrophoresis; all the complexes displayed chemical nuclease activity in the absence and presence of H2O2 via an oxidative mechanism. Complexes 14 inhibit the growth of both Gram-positive and Gram-negative bacteria.  相似文献   

13.
New complexes of Co(II), Ni(II), and Cu(II) nitrates, chlorides, and perchlorates with 4-(4-hydroxyphenyl)-1,2,4-triazole (L) were obtained and examined by single-crystal X-ray diffraction, X-ray powder diffraction, and electronic absorption and IR spectroscopy. The cations of all the complexes have linear trinuclear structures. Ligand L is coordinated to the metal ions in a bidentate bridging fashion through the N(1) and N(2) atoms of the heterocycle. The coordination polyhedron of the metal atoms is a distorted octahedron. The molecular and crystal structures of the complexes [Co3L6(H2O)6](ClO4)6 · 3C2H5OH · 3.75H2O and [M3L6(H2O)6](ClO4)6 · 6H2O (M = Cu2+ and Ni2+) were determined.  相似文献   

14.
A new bisphosphoryl ligand, 2,4-bis(diphenylphosphorylmethyl)mesitylene (L1), has been synthesized. Upon the interaction of L1 with lanthanide nitrates, stable mononuclear chelates [Ln(L1) n (NO3)3] (Ln = Ce(III), Nd(III), Er(III); n = 1, 2) were obtained. The structure of the complexes in solid state and in solution was studied by vibrational (IR and Raman) spectroscopy, X-ray diffraction, and conformational (molecular mechanics) analysis.  相似文献   

15.
The structure of 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol 2,6-[Ph2P(O)CH2]2-4-MeC6H2OH(L1) and its 1: 1 complex with cerium(III) nitrate were studied by X-ray diffraction. A rather strong intramolecular hydrogen bond P=O…H-O (O…O, 2.646(1) Å) exists in the L1 molecules. In the crystal, the molecules are combined into centrosymmetric dimers through the stacking interaction between the central phenol rings; the distance between the ring planes is 3.39 Å. In the complex molecule, [Ce(L1)(NO3)3 · Me2C(O)], the neutral ligand L1 is tridentate and the three nitrate ions are bidentate, and the tenth coordination site is occupied by acetone oxygen. No intramolecular H-bonds are present. In the crystal, the complex molecules are combined into centrosymmetric dimers through intermolecular hydrogen bonds O-H…O-NO2 (O…O, 2.713(8) Å). The vibrational (IR, Raman) spectra of the ligand and the complex were studied and the principal bands were assigned. According to IR spectroscopy, the P=O…H-O intramolecular hydrogen bond is retained in both the ligand and the complex molecules.  相似文献   

16.
The ruthenium tricarbonyl derivative [Ru(CO)3(sha)] (1), was synthesized from reaction of [Ru3(CO)12] with N-salicylidene-2-hydroxyaniline (shaH2) Schiff base. The corresponding reactions of the ruthenium cluster with shaH2 in presence of a secondary ligand L,L?=?pyridine and triphenyl phosphine resulted in the formation of the dicarbonyl derivatives [Ru(CO)2(shaH2)(L)] (2, 3). In the presence of L?=?2-aminobenzimidazole or thiourea, two complexes [Ru(CO)2(sha)(L)] (4, 5) were formed and the shaH2 ligand bonded to ruthenium oxidatively. The bipyridine(bpy) derivative had the molecular formula [Ru(CO)2(shaH)(bpy)] (6), with shaH coordinated bidentate. All complexes were characterized by elemental analysis and mass, IR, 1H NMR and UV–Vis spectroscopy. The spectroscopic studies of these complexes revealed several structural arrangements and different tautomeric forms.  相似文献   

17.
Rhenium(V) complexes of 1H-benzimidazole (L), isolated from acidic media: (HL)2[ReOX5]·(H2O) n and [ReOL x X y (H2O) z ](H2O) n (HL and L are protonated and deprotonated forms of benzimidazole; X = Cl-, Br-) were studied by means of IR spectroscopy, 1H NMR spectroscopy, and thermal analysis.  相似文献   

18.
New heteronuclear complexes containing oxorhenium(V), Cu(II), Ni(II), Fe(III), UO2(VI) and Th(IV) ions were prepared by the reaction of the complex ligand, [ReO(H4L)Cl]Cl2, where H4L = 8,17-dimethyl-6,15-dioxo-5,7,14,16-tetrahydrodibenzo[a,h][14]annulene-2,11-dicarboxylic acid, with the previous transition and actinide salts. Three heteronuclear Cu(II) complexes were isolated depending on the ratio of [ReO(H4L)Cl]Cl2?:?Cu(II) ion. When the ratios were 1?:?0.5, 1?:?1 and 1?:?2, the heteronuclear complexes {[ReO(H3L)Cl]2CuCl2(OH2)2}SO4 · H2O (I), [ReO(H3L)Cl2Cu(OH2)2(SO4)] (II) and {ReO(H2L)Cl[Cu(OH2)3 SO4]2} (III) were obtained, respectively. Heteronuclear complexes of the other metal cations were obtained by mixing [ReO(H4L)Cl]Cl2 with the metal salt in the ratio 1?:?1 to obtain the heteronuclear complexes [ReO(H3L)Cl2Ni(OH2)2](NO3)2 (IV), [ReO(H3L)Cl3Fe(OH2)3](NO3)2 (V), [ReO(H3L)ClUO2(NO3)2 (OH2)]Cl (VI) and [ReO(H3L)Cl3Th(NO3)2(OH2)]NO3 · 2H2O (VII). The complex ligand coordinates with the heterometal ion via the carboxylate group, and the infrared bands νas COO and νs COO indicate that the carboxylate acts as a unidentate ligand to the heterometal cations. Cu(II) and Fe(III) cations in the heteronuclear complexes have octahedral geometry, while Ni(II) is square planar. Thermal studies explored the possibility of obtaining new heteronuclear complexes pyrolytically in the solid state from the corresponding mother complexes. The structures of the complexes were elucidated by conductance, IR and electronic spectra, magnetic moments, 1H NMR and TG-DSC measurements as well as by mass spectroscopy.  相似文献   

19.
Newly designed hetero-dinuclear 3d–4f complex [Cu(L)La (NO3)2(μ-NO3)(H2O)]·EtOH ( 1 ), hetero-tetranuclear 3d–4f complex [Cu(L)Ce (NO3)2(μ-NO3)(OAc)2]2·MeOH ( 2 ) and hetero-multinuclear 3d–4f complexes [{Cu(L)Ln (NO3)3}2][Cu(L)Ln (NO3)3]2 (Ln = Pr ( 3 ) and Nd = ( 4 )) have been self-assembled from the reaction of Cu (OAc)2·H2O, Ln (NO3)3·6H2O (Ln = La, Ce, Pr and Nd) with an unsymmetric salamo-like bisoxime ligand H2L (6-Methoxy-6′-ethoxy-2,2′-[ethylenedioxybis (nitrilomethylidyne)]diphenol) based on a Schiff base condensation of 2-[O-(1-ethoxyamide)]oxime-6-methoxyphenol and 3-ethoxysalicylaldehyde. The structures of complexes 1 – 4 were characterized by elemental analyses, PXRD analyses, IR, UV–Vis spectra, and single-crystal X-ray analyses. In addition, the supramolecular interactions and fluorescence properties of complexes 1 – 4 are discussed in detail. Moreover, the antioxidant activities of the complexes 1 – 4 were determined by superoxide radical-scavenging method in vitro, which indicates that the complexes 1 – 4 all show potential antioxidant properties.  相似文献   

20.
《Polyhedron》1987,6(2):275-279
Several new peroxo complexes of molybdenum and tungsten containing different organic ligands have been prepared. The complexes have the compositions [Mo(O)(O2)L2], [Mo(O)2(O2)L(H3O)]+, [Mo(O)(O2)L′] and [W(O)(O2)L2] [L = oxoquinolino, aniline-2- carboxylate, 2-aminophenoxide, picolinato or 2-carboxylatoquinolino ligand; L′ = N-(2- oxophenyl)salicylidenimino ligand], respectively. The complexes were found to oxidize allyl alcohol, and also PPh3 and AsPh3, to their oxides. The IR spectra of the complexes indicate that the frequency of the v1-mode of the M(O2) grouping, which is essentially an OO stretch, decreases with the increase in atomic number of metals in a particular group.  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