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1.
NbX5 (X = F, 1a; X = Cl, 1b) reacted with γ-butyrolactone (but), ε-caprolactam (cap), δ-valerolactam (val) in 1:1 M ratio in chlorinated solvent, affording either the neutral coordination adducts NbCl5L (L = but, 2a; L = val, 2b) or the ionic ones [NbX4L2][NbX6] (X = F, L = but, 3a; X = F, L = val, 3b; X = F, L = cap, 3c; X = Cl, L = cap, 3d). The reaction of 1a with equimolar amount of guanine (gua) in CH3CN resulted in the formation of the complex [NbF4(gua)2][NbF6], 3e. The addition of two equivalents of organic substrate to 1 gave selectively the compounds NbCl5L2 (L = but, 4a; L = val, 4b) or [NbF4L4][NbF6] (L = but, 5a; L = val, 5b; L = cap, 5c). The 1:2 M reaction of 1b with ε-caprolactam proceeded with C-N bond activation and afforded the derivative , 6, in high yield.  相似文献   

2.
Tuning the substituents of triazoles, we obtained di- and tri-nuclearic triazole-nickel complexes [Ni2(deatrz)4(H2O)5](SO4)2 · 7H2O (1) and [Ni3(dmtrz)6(H2O)6](SO4)3 · 21H2O (2) (deatrz = 3,5-diethanyl-4-amino-1,2,4-triazole; dmtrz = 3,5-dimethanyl-1,2,4-triazole). The X-ray single-crystal diffraction results reveal that sulfate anions and water clusters form supramolecular networks in both complexes. In 1, a supramolecular two-dimensional structure was fabricated by nano-sized grid with novel tetramer water rings templated via binuclear-nickel(II) cations, while in 2, water molecules and sulfate anions construct the first sulfate-water three-dimensional supramolecular network as host to encapsulate trinuclear-nickel guests.  相似文献   

3.
A new family of one-dimensional oxalato-bridged metal(II) complexes with formula {[M(ox)(abpt)]·4H2O}n [MII = Mn (1), Fe (2), Co (3), Zn (4); ox = oxalate dianion; abpt = 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole] has been synthesized and chemically, structurally and magnetically characterized. The crystal structures of compounds 2-4 have been solved by single crystal X-ray diffraction, whereas complex 1 has been studied by means of X-ray powder diffraction methods. All of them are isomorphous and crystallize in the triclinic space group P. The metal atoms are bridged by bis-bidentate oxalate anions forming zig-zag chains in which bidentate chelating abpt ligands complete the octahedral O4N2 donor set. The crystal structures show an open-framework that contains rectangular channels in which easily removable hydrogen bonded ribbons of water molecules are located. The occurrence of antiferromagnetic intrachain interactions for compounds 1-3 was determined by cryomagnetic susceptibility measurements.  相似文献   

4.
Treatment of Rh(acac)(CO)2 (acac = acetoacetonate) with perchloric acid followed by addition of an α-diimine (α-diimine = 1,4-bis(Ar)-2,3-dimethyl-1,4-diaza-1,3-butadiene, Ar = 3,5-dimethylphenyl, 1; 3,5-di-tert-butylphenyl, 2; and 3,4,5-trimethoxyphenyl, 3; phenyl, 4; and 4-chlorophenyl, 5) generates a series of complexes of the type [Rh(α-diimine)(CO)2][ClO4] 6-10 with varying electronic properties of the supporting diimine ligand. X-ray crystal structures have been determined for the α-diimine ligands 1-5, and complexes 6, 8, and 10.  相似文献   

5.
A series of pyrazole-bridged heterometallic 3d-4f complexes, [CuDy(ipdc)2(H2O)4] · (2H2O)(H3O+) (1) and [CuLn(pdc)(ipdc)(H2O)4] · H3O+ (Ln = Ho (2), Er (3), Yb (4); H3ipdc = 4-iodo-3,5-pyrazoledicarboxylic acid; H3pdc = 3,5-pyrazoledicarboxylic acid), {[Cu3Ln4(ipdc)6(H2O)16] · xH2O}n (Ln = Sm (5), x = 8.5; Ln = Eu (6), x = 7; Ln = Gd (7), Tb (8), x = 9), have been synthesized and structurally characterized. Ligand H3ipdc was in situ obtained by iodination of ligand H3pdc. Complexes 1-4 are pyrazole-bridged heterometallic dinuclear complexes, and 2-4 are isostructural. Complexes 5-8 are isostructural and comprised of an unusual infinite one-dimensional tape-like chain based on pyrazole-bridged heterometallic dinuclear units. The magnetic properties of compounds 1-4, 7 and 8 have been investigated through the magnetic measurement over the temperature range of 1.8-300 K.  相似文献   

6.
Two new pyrazole-derived ligands, 1-ethyl-3,5-bis(2-pyridyl)pyrazole (L1) and 1-octyl-3,5-bis(2-pyridyl)pyrazole (L2), both containing alkyl groups at position 1 were prepared by reaction between 3,5-bis(2-pyridyl) pyrazole and the appropriate bromoalkane in toluene using sodium ethoxide as base.The reaction between L1, L2 and [MCl2(CH3CN)2] (M = Pd(II), Pt(II)) resulted in the formation complexes of formula [MCl2(L)] (M = Pd(II), L = L1 (1); M = Pd(II), L = L2 (2); M = Pt(II), L = L1 (3); M = Pt(II), L = L2 (4)). These complexes were characterised by elemental analyses, conductivity measurements, infrared, 1H, 13C{1H} NMR and HMQC spectroscopies. The X-ray structure of the complex [PtCl2(L2)] (4) was determined. In this complex, Npyridine and Npyrazole donor atoms coordinate the ligand to the metal, which complete its coordination with two chloro ligands in a cis disposition.  相似文献   

7.
Four new triorganotin complexes of 3-amino-5-mercapto-1,2,4-triazole with the type of R3Sn(SC2N3HNH2-3) (R = Me, 1; n-Bu, 2; Ph, 3; PhCH2, 4) have been synthesized. All the complexes have been characterized by elemental analysis, IR, 1H NMR and 13C NMR spectra. Complexes 1, 3 and 4 have been characterized by X-ray crystallography analyses too. The geometry about Sn of complex 1 is distorted trigonal bipyramidal and the supramolecular structures of complex 1 has been found consist of channels built up by intermolecular N-H?N hydrogen bonding. The geometry of tin atoms in complexes 3 and 4 are distorted tetrahedron and 1D polymers connected by intermolecular N-H?N hydrogen bonding or N-H?N and N-H?S hydrogen bonding. Additionally, 1D polymer of complex 3 aggregated in 2D layer by intermolecular N-H?S hydrogen bonding.  相似文献   

8.
The bis(pyrazol-1-yl)azine ligands 2,3-bis(pyrazol-1-yl)quinoxaline (bpzqnx), 2,3-bis(pyrazol-1-yl)pyrazine (bpzprz) and 3,6-bis(3,5-dimethylpyrazol-1-yl)pyridazine (bpz*pdz) were prepared by the reaction of pyrazolate salts and the corresponding azine dichloride derivatives. The reaction of these ligands with Ru(arene) precursors led to the mononuclear complexes [RuCl(arene)(L)]BPh4 (arene = p-cymene, L = bpzqnx, 1, bpzprz, 5, bpz*pdz, 7; arene = C6H6, L = bpzqnx, 2, bpzprz, 6, bpz*pdz, 8) with the N-donor ligand coordinated in a bidentate chelate way. In general, the ligands coordinate through one pyrazole ring and the azine, except in the cases of 1 and 2 where the two pyrazolyl rings are coordinated to the metal in a symmetrical way. When the reactions between the ruthenium precursors and bpzqnx are carried out in MeOH, the complexes [RuCl(arene)(OMepzqnx)]BPh4 with partially methanolyzed ligands are isolated (arene = p-cymene, 3; C6H6, 4). In this process a methoxy group has replaced one of the pyrazole groups in the ligand. The X-ray structures of 6 and 7 have been determined. These compounds have a three-legged piano-stool structure with cations and anions packed through weak interactions. Complexes 1-8 are active in ketone hydrogenation transfer processes even in the absence of base.  相似文献   

9.
Nine triorganotin(IV) complexes of the type R3SnL (L = L1 R = Me 1, Ph 2, PhCH23; L = L2 R = Me 4, Ph 5, PhCH26; L = L2 R = Me 7, Ph 8, PhCH29) have been obtained by reaction of new Schiff base HL1, HL2 or HL3 with triorganotin(IV) chloride in the presence of sodium ethoxide. All the complexes 1-9 were characterized by elemental, IR and NMR spectra analyses. Except for complexes 3, 4, 6, 9, the others were also characterized by X-ray crystallography diffraction analyses, which revealed that complexes 1, 2, 5, 7, 8 were four coordinated and displayed a capped tetrahedron.  相似文献   

10.
The reactivity of hybrid scorpionate/cyclopentadienyl ligand-containing trichloride zirconium complexes [ZrCl3(bpzcp)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and [ZrCl3(bpztcp)] (2) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl] toward several lithium alkoxides has been carried out. Thus, alkoxide-containing complexes [ZrCl2(OR)(bpzcp)] (R = Me, 3; Et, 4; iPr, 5; (R)-2-Bu, 6), [ZrCl2(OR)(bpztcp)] (R = Me, 7; Et, 8; iPr, 9; (R)-2-Bu, 10) and [Zr(OR)3(bpztcp)] (R = Et, 11; iPr, 12) were prepared by deprotonation of the appropriate alcohol group with BunLi followed by reaction with 1 or 2. In addition, the imido-complex [Ti(NtBu)Cl(bpztcp)(py)] (13) were also prepared. The structures of these complexes have been proposed on basis of spectroscopic and DFT methods.  相似文献   

11.
A novel binuclear copper(II) complex [Cu2L(μ-SO4)](PF6)2 (1) (L = 3,5-bis (bis(pyridine-2-ylmethyl)amino)methyl)-4H-1,2,4-triazol-4-amine) has been synthesized and structurally characterized. X-ray structure shows that the two copper(II) atoms are bridged by one bidentate sulfate ion and the 1,2,4-triazole ring of L with Cu1?Cu2 distance of 4.404 Å. Each copper(II) center has a distorted trigonal-bipyramidal configuration. Variable-temperature magnetic susceptibility studies (2-300 K) indicate the existence of weak antiferromagnetic coupling between the copper(II) ions in complex 1. The interaction of complex 1 with calf thymus DNA (CT-DNA) has been studied by UV absorption, fluorescence spectroscopy, circular dichroism spectroscopy, viscosity and cyclic voltammetry. Furthermore, complex 1 was able to promote single and double strand DNA cleavage in both aerobic and anaerobic conditions, the pseudo-Michaelis-Menten kinetic parameters kcat = 2.58 h−1 and Km = 1.2 × 10−4 M were obtained for 1. The hydrolytic cleavage of DNA by the complex was supported by the evidence from free radical quenching, anaerobic experiment, thiobarbituric acid-reactive substances (TBARS) assay.  相似文献   

12.
Consecutive synthesis methodologies for the preparation of a series of copper(I) formates [LmCuO2CH] (L = nBu3P: 4a, m = 1; 4b, m = 2; 5, L = [Ti](CCSiMe3)2, m = 1, [Ti] = (η5-C5H4SiMe3)2Ti) and [LmCuO2CH·HO2CR] (L = nBu3P: 7a, m = 1, R = H; 7b, m = 2, R = H; 7c, m = 2, R = Me; 7d, m = 2, R = CF3; 7e, m = 2, R = Ph. L = (cC6H11)3P, R = H: 8a, m = 2; 8b, m = 3. L = (CF3CH2O)3P, R = H: 9a, m = 2; 9b, m = 3. L = (CH3CH2O)3P, R = H: 10a, m = 2; 10b, m = 3. L = [Ti](CCSiMe3)2; m = 1: 11a, R = H; 11b, R = Ph) is reported using [CuO2CH] (1) and L (2a, L = nBu3P; 2b, L (cC6H11)3P; 2c, L = (CF3CH2O)3P; 2d, L = (CH3CH2O)3P; 3, L = [Ti](CCSiMe3)2) as key starting materials. Addition of formic acid (6a) or carboxylic acid HO2CR (6b, R = Me; 6c, R = CF3; 6d, R = Ph) to the afore itemized copper(I) formates 4 and 5 gave metal-organic or organometallic 7-11. The molecular structures of 8a and 11a in the solid state are reported showing a threefold coordinated copper(I) ion, setup by either two coordinatively-bonded phosphorus atoms and one formate oxygen atom (8a) or two π-bonded alkyne ligands and one oxygen atom (11a). A formic acid molecule is additionally hydrogen-bonded to the CuO2CH moiety. The use of 7b as suitable precursor for the deposition of copper onto TiN-coated oxidized silicon wafers by the spin-coating process below 300 °C is described. Complex 7b offers an appropriate transformation behavior into metal phase by an elimination-decarboxylation mechanism. The morphology of the copper films strongly depends on the annealing conditions. A closed grain network densified by a post-treatment is obtained (8 °C min−1, N2/H2 carrier gas). Hydrogen post-anneal to 420 °C after film deposition gave a copper film showing resistivities from 2.5 to 3.7 μΩ cm. This precursor was also used for gap-filling processes.  相似文献   

13.
Neutral dioxovanadium (V) complexes [VO2(HL)] (H2L = I: 1, H2L = II: 2 and H2L = III: 3; H2L are the thiosemicarbazones H2pydx-tsc (I), H2pydx-chtsc (II) and H2pydx-clbtsc (III); pydx = pyridoxal, tsc = thiosemicarbazide, chtsc = N4-cyclohexylthiosemicarbazide, clbtsc = N4-(2-chloro)benzylthiosemicarbazide) have been isolated and characterised on the basis of elemental and electrochemical analyses, spectroscopic (IR, UV-Vis, 1H and 51V NMR) data, thermogravimetric studies and reactivity patterns. These complexes are stable in solution at ambient temperature but heating of the methanolic solutions yields the μ-oxo binuclear complexes [(VOL)2μ-O] (H2L = I: 4, H2L = II: 5, H2L = III: 6). Treatments of dioxo species with H2O2 yield oxoperoxo species, the formations of which have been established spectrophotometrically. Similarly, the formations of oxohydroxo species, an intermediate proposed during the catalytic action of haloperoxidases, have also been established in solution by treating 1, 2 and 3 with a methanolic solution of HCl. The antiamoebic activities were carried out to ascertain the effectiveness of dioxovanadium(V) and μ-oxobis(oxovanadium(V)) complexes in comparison to their corresponding thiosemicarbazones. These complexes possess noteworthy potencies against HM1:1MSS strain of Entamoeba histolytica. Complexes 2, 3, 5 and 6 showed less IC50 values than metronidazole, indicating that these metal thiosemicarbazones may be the lead molecules to inhibit the growth of E. histolytica. Within the series, complex 5 showed the most promising amoebicidal activity (IC50 = 0.5 μM versus IC50 = 1.8 of metronidazole).  相似文献   

14.
A 2D layer complex 1 and a linear trinuclear complex 2 with mixed ligands have been synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction. In 1, the Mn(II) ions are six-coordinated and lie in distorted octahedron coordination environments. Complex 1 is connected into a 2D layer structure based on a linear trinuclear Mn3(admtrz)4(N3)6 (admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole) building unit with either (6,3) topology when Mn1 cations as three-connected nodes or (4,4) network when the coordination trinuclear units being regarded as four connected nodes. In 2, the Co(II) ions are in slightly distorted octahedron coordination geometries. The magnetic behaviors are investigated in the temperature range 1.8-300 K. The magnetic susceptibility measurements show that the Mn(II) ions of complex 1 are weakly antiferromagnetically coupled with g = 1.98(1), J1 = −6.31(5) cm−1 and J2 = −1.88(1) cm−1. There is dominant zero field splitting (ZFS) effects with g values, g// = 2.38(2) and g = 4.96(4), indicated a significant presence of the spin-orbit coupling and magnetization experiment reveals large, uniaxial zero-field splitting parameters of D = −29.55 cm−1 for 2.  相似文献   

15.
Two unprecedented families of bpca-based mono-dimensional complexes Cu(bpca)(X) (X = CN, 1; N3, 2) and [Cu1 − xFex(bpca)](ClO4) (x = 0, 3; 0.23, 4) were synthesised. The structure of 1 was solved ab initio from X-ray powder diffraction data and refined by Rietveld methods. The complexes 3-4 were characterised by X-ray single crystal diffraction. In 1 the cyano ligand coordinates the metal centres, the Cu centres forming a zigzag 1-D chain along the (0 0 1) direction, while in 3-4, the bpca ligand itself acts as the link towards the metal ions which are arranged in a linear 1-D chain running parallel to the (0 0 1) direction. An infrared spectroscopy study confirmed these coordination modes. The magnetic properties of both chain families were studied. 1-2 do not show significant magnetic interactions, whereas the magnetic behaviour for 3-4 suggests dominant antiferromagnetic interactions between the metal ions within the chains. The magnetic behaviour of 3 was analysed using the Padé approximation of the Bonner-Fisher model for S = 1/2 antiferromagnetic chains. The J value was estimated as 10 K.  相似文献   

16.
Eight triorganotin complexes of the types [(R3Sn)2(C24H16N8S2)].Y (R = Ph, Y = 0 (1); R = PhCH2, Y = 2CH3OH (2); R = n-Bu, Y = 0 (3)), [(R3Sn)2(C24H16N8S2)]n (R = Me (4)), [(R3Sn)2(C12H6N6S4)] · Y (R = Ph, Y = CH2Cl2 (5); R = PhCH2, Y = 0 (6)) and [(R3Sn)2(C12H6N6S4)] (R = Bu (7), R = Me (8)) have been obtained by H2L1 (H2L1 derived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol) and H2L2 (H2L2 derived from 5-amino-1,3,4-thiadiazole-2-thiol) with triorganotin chloride in the presence of sodium ethoxide. All the complexes were characterized by elemental, IR and NMR spectra analyses, except for complexes 1, 3, 6 and 8, other complexes were also characterized by X-ray diffraction analyses, which reveal that complexes 2 and 5 are dinuclear structures, complex 4 has a 2D network structure and complex 7 forms a macrocyclic structure linked by intermolecular N → Sn interactions.  相似文献   

17.
A family of bis(2-amino-3,5-dihalopyridine)dihalocopper(II) compounds has been synthesized, including (3,5-diCAP)2CuCl2 (1), (3,5-diCAP)2CuBr2 (2), (3,5-diBAP)2CuCl2 (3), and (3,5-diBAP)2CuBr2 (4) [3,5-diCAP = 2-amino-3,5-dichloropyridine; 3,5-diBAP = 2-amino-3,5-dibromopyridine]. These complexes have been analyzed through single crystal X-ray diffraction and temperature dependant magnetic susceptibility. The compounds are all isostructural, forming bi-bridged chains with long Cu-X?Cu bridges in the crystal lattice. The two copper chloride compounds (1 and 3) exhibit weak antiferromagnetic interactions along these chains.  相似文献   

18.
Synthesis of complexes with the formulations [M(CPI)2Cl2] (M = Zn, 1; M = Cd, 4) and [M(CPI)6](X)2 (M = Zn, X = NO3, 2; X = ClO4, 3; M = Cd, X = NO3, 5; X = ClO4, 6) have been achieved from the reactions of MCl2, M(NO3)2·xH2O and M(ClO4)2·xH2O (M = Zn, Cd) with 1-(4-cyanophenyl)-imidazole (CPI). Complexes 1-6 have been characterized by elemental analyses and spectral studies (IR, 1H, 13C NMR, electronic absorption and emission). Molecular structures of 1, 2, 3 and 6 have been determined crystallographically. Weak interaction studies on the complexes revealed presence of various interesting motifs resulting from C-H···N, C-H···Cl and π-π stacking interactions. The complexes under study exhibit strong luminescence at ∼450 nm in DMSO at room temperature.  相似文献   

19.
New scandium and yttrium complexes ScL2(bpzmp)(THF) {L = Cl (1); L = CH2Si(CH3)3 (3)}, YL2(bpzmp) {L = Cl (2); L = OTf (5)} and Y(CH2SiMe3)2(bpzmp)(THF) (4) bearing the heteroscorpionate bpzmp ligand {bpzmp = (3,5-tBu2-2-phenoxo)bis(3,5-Me2-pyrazol-1-yl)methane} have been synthesized and characterized by means of NMR and Mass spectroscopy. The tridentate monoanionic ligand resulted κ3-coordinated to the metal via the oxygen and both the sp2 nitrogen atoms of the heterocycles, producing complexes in CS symmetry.The behavior of 1-4 in ethylene polymerization was investigated after proper activation with different activating agents. Complex 4, in combination with the Brönsted or Lewis acids [PhNMe2H][B(C6F5)4] or [Ph3C][B(C6F5)4], produced linear high molecular weight polyethylene in good yield.  相似文献   

20.
A novel 2D MOF material [Cd2(AmTRZ)2·I3]·(R4N+)] (1; AmTRZ = 3-amino-1,2,4-triazole, R4N+ = tetraethylammonium), with an anionic skeleton has been hydrothermally synthesized in presence of an ionic liquid, tetraethylammonium hydroxide. 1 is endowed with large helical porous channels and two cadmium metal centers with different coordination environment around them besides showing presence of an unprecedentedly ordered extra-framework layer pattern of the encapsulated Et4N+ counter cations.  相似文献   

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