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1.
Reactions of HgX2 (X?=?Cl, N3, NO3) with (E)-2-methoxy-N-(pyridin-2-ylmethylene)aniline (L1) and (E)-4-methoxy-N-(pyridin-2-ylmethylene)aniline (L2) in ethanol gave two monomers, [HgL1(Cl)2] (1) and [HgL2(NO3)2(DMSO)] (5), and three coordination polymers, {[HgL1(N3)2]2·Hg(N3)2}n (2), [HgL2(Cl)2]n (3), and [HgL2(NO3)2]n·nCH3CN (4). Compounds 1–5 were characterized by elemental analysis, IR, NMR spectroscopy, and single-crystal X-ray diffraction. The common feature of monomeric 1 and 5 is the presence of intra- and intermolecular Hg–O bonds. In the absence of these, polymeric structures arise as a result of azide, chloride, and nitrate bridging in 2, 3, and 4, respectively. Fluorescent properties of 1–5 were also investigated.  相似文献   

2.
Two new N2O2 unsymmetrical Schiff bases, H2L1 = 3-[({o-[(E)-(o-hydroxyphenyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol and H2L2 = 3-[({o-[(E)-(2-hydroxy-1-naphthyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol, and their copper(II) and nickel(II) complexes, [CuL1] (1), [CuL2] (2), [NiL1] (3), and [NiL2] (4), have been synthesized and characterized by elemental analyses and spectroscopic methods. The crystal structures of these complexes have been determined by X-ray diffraction. The coordination geometry around Cu(II) and Ni(II) centers is described as distorted square planar in all complexes with the CuN2O2 coordination more distorted than the Ni ones. The electrochemical studies of these complexes indicate a good correlation between the structural distortion and the redox potentials of the metal centers. The ligand and metal complexes were also screened for their in vitro antibacterial activity.  相似文献   

3.
Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HLpz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HLpz?) were synthesized and characterized. The X-ray crystal structures of [Cu2(Lpz)2(4,4?-bipy)(OTf)2] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(Lpz)(py)2]OTf·H2O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(Lpz)(μ2-1,1-N3)]n (3), [Cu(Lpz?)(μ2-1,3-N3)]n (4), and [Cu(HLpz)Cl]n (5) are coordination polymer 1-D chains in the solid state.  相似文献   

4.
Three new centrosymmetric dinuclear copper(II) complexes, [Cu2Cl2(L1)2] (1), [Cu2(μ 1,3-NCS)2(L2)2] (2), and [Cu2(μ 1,1-N3)2(L3)2] (3), where L1, L2, and L3 are the deprotonated forms of the Schiff bases 1-[(2-propylaminoethylimino)methyl]naphthalen-2-ol (HL1), 1-[(3-methylaminopropylimino)methyl]naphthalen-2-ol (HL2), and 2-[(2-isopropylaminoethylimino)methyl]phenol (HL3), respectively, have been prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Each Cu is coordinated by the three donors of the Schiff bases and by two bridging groups, forming a square-pyramidal geometry.  相似文献   

5.
The reaction of [ZnCl2] with N-cyclopentyl-1-(quinolin-2-yl)methanimine (LA), N-cyclohexyl-1-(quinolin-2-yl)methanimine (LB), N-cyclohexyl-1-(pyridin-2-yl)methanimine (LC), 2,6-diethyl-N-(pyridin-2-ylmethylene)aniline (LD), N-cyclopentyl-1-(pyridin-2-yl)methanimine (LE), and N-phenyl-(pyridin-2-yl)methanimine (LF) in ethanol produced the bidentate [(NN′)ZnCl2] complexes, [LAZnCl2], [LBZnCl2], [LCZnCl2], [LDZnCl2], [LEZnCl2] and [LFZnCl2], respectively. The molecular structures revealed that the zinc in [LnZnCl2] (Ln = LA ? LD) showed a distorted tetrahedral geometry involving two nitrogens of N,N’-bidentate ligands and two chloride ligands. Most of these initiators were effective for polymerization of methyl methacrylate (MMA) and polymerization of rac-lactide (rac-LA). [LCZnCl2] (with N-cyclohexyl substituted at imine-pyridine moiety) exhibited the highest catalytic activity for MMA polymerization in the presence of modified methylaluminoxane (MMAO) with an activity of 3.33 × 104 g PMMA/mol·Zn·h at 60 °C, giving moderate syndiotactic poly methyl methacrylate (PMMA) with high molecular weight (9.62 × 105 g/mol). The dimethyl derivatives [LnZnMe2] (Ln = LA ? LF), generated in situ, polymerized rac-LA with moderate activity and yielded a polylactide (PLA) with good number-average molecular weights and narrower polydispersity indices (PDIs). [LAZnMe2] effectively initiates the ring-opening polymerization (ROP) of rac-LA to attain heterotactic PLA (Pr = 0.91).  相似文献   

6.
《Journal of Coordination Chemistry》2012,65(16-18):2856-2874
Abstract

Nine new cobalt(II) compounds, trans-[Co(LPAQ)2(Py)2] (1), trans-[Co(LPAQ)2(3-MePy)2] (2), trans-[Co(LMeAQ)2(Py)2] (3), trans-[Co(LOMeAQ)2(Py)2] (4), trans-[Co(LOEtAQ)2(Py)2]·2(H2O) (5), trans-[Co(LCAQ)2(Py)2] (6), trans-[Co(LBAQ)2(Py)2] (7), cis-[Co(LBAQ)2(3-MePy)2] (8a) and trans-[Co(LBAQ)2(3-MePy)2]·2(3-MePy) (8b) (primary ligand: LXAQ?=?substituted 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-olate; secondary ligands: Py?=?pyridine, 3-MePy = 3-methylpyridine), have been synthesized and characterized by elemental analysis, IR and UV-vis spectroscopy. Magnetic measurements of the cobalt compounds were performed in solution by 1H NMR spectroscopy using the Evans’ method while their redox properties were studied by cyclic voltammetry. Single-crystal X-ray diffraction analysis of the compounds revealed their octahedral geometries and trans configuration, except for 8a, which has a cis configuration. Intermolecular noncovalent interactions were detected, π···π interactions in 5, C?–?H···π interactions in 2 and C?–?H···π edge-to-face (T-shaped) arrangements in 3, 4, 6, and 7.  相似文献   

7.
Two new complexes, {[PbL(NO3)2H2O]H2O}n (1) and [BiL2(NO3)2]NO3 (2), based on (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine (L) were synthesized and characterized by IR spectra, single-crystal X-ray diffraction, and elemental analyzes. X-ray single crystal diffraction experiments of 1 and 2 display that extensive hydrogen bonds and ππ stacking interactions construct the 1-D infinite chain {[PbL(NO3)2H2O]H2O}n and [BiL2(NO3)2]NO3 into two 3-D supramolecular frameworks. Interestingly, pure phase PbO nano-particles were synthesized by thermolysis of 1 and characterized by scanning electron microscopy and X-ray powder diffraction analyzes. Furthermore, antioxidant activities of L, 1, and 2 were also studied.  相似文献   

8.
Herein, we explore the coordination of di- and triimine chelators at ruthenium(II) and ruthenium(III) centers. The reactions of 2,6-bis-((4-tetrahydropyranimino)methyl)pyridine (thppy), N1,N2-bis((3-chromone)methylene)benzene-1,2-diamine (chb), and tris-((1H-pyrrol-2-ylmethylene)ethane)amine (H3pym) with trans-[RuIICl2(PPh3)3] afforded the diamagnetic ruthenium(II) complex cis-[RuCl2(thppy)(PPh3)] (1) and the paramagnetic complexes [mer-Ru2(μ-chb)Cl6(PPh3)2] (2), and [Ru(pym)] (3), respectively. The complexes were characterized by IR, NMR, and UV–vis spectroscopy and molar conductivity measurements. The structures were confirmed by single crystal X-ray diffraction studies. The redox properties of the metal complexes were probed via cyclic- and squarewave voltammetry. Finally, the radical scavenging capabilities of the metal complexes towards the NO and 2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl (DPPH) radicals were investigated  相似文献   

9.
Four new mononuclear complexes, [Ni(L1)(NCS)2] (1), [Ni(L2)(NCS)2] (2), [Co(L1)(N3)2]ClO4 (3), and [Co(L2)(N3)2]ClO4 (4), where L1 and L2 are N,N′-bis[(pyridin-2-yl)methylidene]butane-1,4-diamine and N,N′-bis[(pyridin-2-yl)benzylidene]butane-1,4-diamine, respectively, have been prepared. The syntheses have been achieved by reaction of the respective metal perchlorate with the tetradentate Schiff bases, L1 and L2, in presence of thiocyanate (for 1 and 2) or azide (for 3 and 4). The complexes have been characterized by microanalytical, spectroscopic, single crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 14 are distorted octahedral geometries. The antibacterial activity of all the complexes and their constituent Schiff bases have been tested against Gram-positive and Gram-negative bacteria.  相似文献   

10.
Treatment of [Ru(PPh3)3Cl2] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl3(κ2-N,N-NH2CH2CH2NMe2)(PPh3)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh3)3], [Ru(CO)2Cl2] or [Ru(tht)4Cl2] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ3-N,N,O-L)(CO)(PPh3)] (2), [RuCl(κ3-N,N,O-L)(CO)2] (3), and a ruthenium(III) complex [RuCl2(κ3-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH2Cl2, 2·CH2Cl2, 3 and 4 have been determined by single-crystal X-ray diffraction.  相似文献   

11.
2‐(Methylthio)aniline (H2L1) and 2‐(phenylthio)aniline (H2L2) were treated with n‐butyllithium to yield the corresponding anilides [LiHL1] and [LiHL2]. Recrystallization from diethyl ether and THF afforded the solvates [LiHL1(Et2O)] and [LiHL2(THF)2]. The X‐ray crystal structure determination revealed dimeric molecules which exhibit a centrosymmetric Li2N2 ring. In the case of [LiHL1(Et2O)] the SMe group is involved in Li coordination and in the case of [LiHL2(THF)2] the SPh group is part of an intramolecular N–H ··· S hydrogen bridge. The sodium anilides [NaHL1(DME)] and [NaHL2(DME)] were obtained from the reaction of H2L1 and H2L2 with sodium amide in DME as solvent. Like in the case of the lithium amides the sodium derivatives [NaHL1(DME)] and [NaHL2(DME)] display centrosymmetric Na2N2 cores. The coordination sphere of the sodium atoms is completed by DME molecules, which act as chelating ligands. In the case of [NaHL1(DME)] the DME molecules enable additionally a linkage of the dimeric subunits to give a chain structure. The potassium derivatives [KNHL1] and [KNHL2(DME)] were obtained from H2L1 and H2L2 and potassium hydride in DME as solvent. [KNHL1] displays a distinct structure based on [(KNHL1)2] dimers, which are linked by additional [KNHL1] units to give a 3D coordination polymer with {4.8.16(3)} topology. [KNHL2(DME)] forms dimers linked by bridging DME molecules to give a chain‐like coordination polymer.  相似文献   

12.
Two new oxovanadium(V) complexes, [VOL1(OEt)(EtOH)] (1) and [VOL2(OMe)(MeOH)] (2), were prepared by reaction of [VO(acac)2] (where acac?=?acetylacetonate) with N′-(3-bromo-2-hydroxybenzylidene)-4-methylbenzohydrazide (H2L1) in ethanol and N′-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide (H2L2) in methanol, respectively. Crystal and molecular structures of the complexes were determined by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. The V ions have octahedral coordination. Thermal stability and the inhibition of urease of the complexes were studied.  相似文献   

13.
New complexes of cobalt(III) with the tridentate and tetradentate Schiff base ligands: 3-methoxy-2-{(Z)[(2-hydroxyphenyl)imino]methyl}phenol (H2L1), 4-[(2-hydroxyphenyl)imino]-2-pentanone (H2L2); and 2-((E)-1-(2-((E)-1-(2-hydroxy-4,5-dimethylphenyl)ethylideneamino)ethylimino)ethyl)-4,5 dimethylphenol (H2L3), namely [CoIII(L1)(N-MeIm)3]PF6 (1), [CoIII(L1)(py)3]ClO4 (2), [Co(L1)(py)3][Co(L1)2] (3) and [CoIII(L2)(N-MeIm)3]PF6 (4) and [Co(L3)(N-MeIm)2]PF6 (5), were synthesized and characterized by physico-chemical and spectroscopic methods. The crystal structures of the complexes were determined by X-ray crystallography. In each of these complexes, the cobalt(III) centre has a slightly distorted octahedral environment, utilizing all available coordination centres of the ligands. The complexes were also screened for in vitro antibacterial activities against four human pathogenic bacteria, and their minimum inhibitory concentrations indicated good antibacterial activities.  相似文献   

14.
Abstract

The reaction of 2,6-bis(benzoxazolyl)-4-tert-butylphenol (HL) with [nBuxSnCl4?x] (x?=?0, 1) in 1:1 stoichiometry yielded the tin coordination complexes [(HL)SnnBuxCl4?x] [x?=?0 (1); x?=?1 (2)]. Deprotonation of HL was performed using reagents having groups with high basicity such as nBuLi or [Sn{N(SiMe3)2}2]. These basic reagents prompted the coordination of the ligand in its anionic form, yielding the complexes [(thf)2Li(L)SnCl4] (3) and [(L)Sn{N(SiMe3)2}] (4), respectively. The molecular structure of HL displayed an intramolecular hydrogen bond OH—N and a planar arrangement of the bis(benzoxazolyl)phenolic system. In the molecular structures of both complexes containing HL an intramolecular hydrogen bond of NH—O type was also present. The coordination of the ligand in either neutral or anionic form is described by a κON chelate mode toward Sn. All complexes displayed bis(benzoxazolyl)phenolic moieties close to planar; the least planar system was observed in 4 that was also studied by DFT methods.  相似文献   

15.
Naphthaldimines containing N2O2 donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H2L1)PtCl2]·3H2O (1) and [(H2L3)2Pt2Cl4]·5H2O (3), or monobasic [(HL2)2Pt2Cl2]·2H2O (2) and [(HL4)2Pt]·2H2O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L1)Pt2Cl4(OH)2]·2H2O (5), [(L2)Pt3Cl10]·3H2O (6), [(L3)Pt2Cl4(OH)2]·C2H5OH (7) and [(L4)Pt2Cl6]·H2O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.  相似文献   

16.
Three mercury(II) complexes containing double-betaine and halide ligands, [(HgCl2)2(L1)] n (1), [(HgBr2)2(L1)(H2O)2] n (2), and [2HgCl2(HL1)·Hg2Cl6] n (3) [L1=O2CCH2N+(CH2CH2)3-N+H2CO2 ], have been prepared and shown to have polymeric structures by single-crystal X-ray analysis. Complex (1) exhibits an infinite zigzag chain in which each mercury(II) atom is coordinated by pairs of carboxylate oxygen atoms and chloride ligands in a distorted tetrahedral geometry. In complex (2), the mercury(II) atom is in an unusual square-planar coordination geometry, and weak mercury-ligand and hydrogen bonding extend the structural skeletons into a three-dimensional network. Complex (3) consists primarily of an assembly of HgCl2(HL1) moieties and [Hg2Cl6] anions, and the mercury(II) atoms are in planar T-shaped and distorted tetrahedral coordination environments, respectively. The resulting three-dimensional network is based on the cross-linkage of nearly planar, wide ribbons running in thea direction.  相似文献   

17.
The reactions of palladium(II) salts with 2-mercaptobenzimidazole (HL) and its 5,6-difluorinated derivative (HLF) were investigated. In the presence of hydrochloric acid, PdCl2 and K2PdCl4 react with HL and HLF in the ethanol—water and acetonitrile—water systems to form the mono-nuclear dicationic complexes [Pd(HL)4]Cl2 (1) and [Pd(LF)4]Cl2 (2). In the absence of HCl, the reactions afford the tetranuclear complex Pd4[(L)23-S,N-(L))2S,N-(L))4] (3). The reaction of triethylamine with an ethanolic solution of 3 leads to degradation of 3 and the formation of the lantern-type dinuclear complex Pd2[(μ2-(L)4] (4), in which the palladium atoms are in the nonequivalent coordination environment, PdN4 and PdS4. The reaction of K2PdCl4 with HL or HLF in the THF—water or acetonitrile—water systems (for the reaction with HLF) in the presence of Et3N produces the lantern-type dinuclear complexes Pd2[(μS,N′-(L3))4] and Pd2[(μ-S,N′-(LF))4] (5), in which the metal atoms are in the equivalent coordination environment (cis-PdN2S2). Dedicated to Academician G. A. Tolstikov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 45–52, January, 2008.  相似文献   

18.
[MNCl2(PPh3)2] complexes (M = Re, Tc) react with N‐[(dialkylamino)(thiocarbonyl)]‐N′‐(2‐hydroxyphenyl)benzamidines (H2L1) with formation of neutral, five‐coordinate nitrido complexes of the composition [MN(L1)(PPh3)]. The products have distorted square‐pyramidal coordination spheres with each a tridentate, double‐deprotonated benzamidine and a PPh3 ligand in their basal planes.  相似文献   

19.
New MnII/CuII/ZnII complexes [(L1)MnCl2] (1), [(L2)CuCl2]·0.5H2O (2) and [(L2)ZnCl(H2O)][ClO4] (3), containing (2-pyridyl)alkylamine ligands, N-methyl-N,N-bis(2-pyridylmethyl)amine (L1) and methyl[2-(2-pyridyl)ethyl](2-pyridylmethyl)amine (L2), have been prepared and characterized, including X-ray crystallography. The most striking feature of the structures of these complexes is the formation of molecular ladder and lamellar topology through the crystal packing arrangement, determined by both strong O–H···Cl and weak (however, multiple) C–H···Cl hydrogen-bonding interactions, to maintain the neutral/cationic metal-ligand coordination units linked to each other. In 3, additional secondary interactions are observed involving coordinated solvent and the counter-ion. The results presented here demonstrate that (i) the choice of organic ligands to provide flexibility and inherent potential to participate in hydrogen-bonding interactions, (ii) the coordination geometry preferences of metal ions, (iii) the number of metal-bound chloride ion and (iv) the presence of solvent/counter-anion have a great influence on supramolecular network topology.  相似文献   

20.
The reaction of [(η5-C5Me5)M(μCl)Cl]2 with the ligand (LL) in the presence of sodium methoxide yielded compounds of general formula [(η5-C5Me5)M(LL)Cl] (1–10) (where M = Ir or Rh and LL = NO or OO chelate ligands). Azido complexes of formulation [(η5-C5Me5)M(LL)N3] (11–20) have been prepared by the reaction of [(η5-C5Me5)M(μN3)(X)]2 (X = Cl or N3) with the corresponding ligands or by the direct reaction of [(η5-C5Me5)M(LL)Cl] with NaN3. These azido complexes [(η5-C5Me5)M(LL)N3] undergo 1,3-dipolar cycloaddition reaction with substituted alkynes in CH2Cl2 and for the first time in ethanol at room temperature to yield iridium (III) and rhodium (III) triazoles (21–28). The compounds were characterized on the basis of spectroscopic data, and the molecular structures of 2 and 26 have been established by single crystal X-ray diffraction.  相似文献   

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