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1.
Syntheses, characterizations, electrochemistry and catalytic properties for styrene epoxidation of three manganese(III) compounds [MnIIIL1(H2O)(MeOH)](ClO4) (1) [MnIIIL1(N3)(H2O)]·dmf (2) [MnIIIL1(Cl)(H2O)] (3) derived from the Schiff base compartmental ligand N,N′-o-phenylenebis(3-ethoxysalicylaldimine) (H2L1) are reported. The three compounds are characterized by elemental analyses, IR, mass and UV–Vis spectra and conductance values. Single crystal X-ray structures of 1 and 2 have been determined. The structures of 1 and 2 show that these are mononuclear compounds having a salen type structure. In both structures, a dinuclear species is formed by bifurcated hydrogen bonding involving coordinated water molecule. The coordination of chloride in 3 is shown by conductance measurements. The compounds have also been characterized by UV–Vis and mass spectroscopic studies. Cyclic voltammetric and square wave voltammetric studies of the three compounds reveal that these undergo Mn(III)/Mn(II) reduction reversibly with the order of the ease of reduction as 3 > 2 > 1. This order has been explained proposing the composition of active species in solution. Catalytic properties for epoxidation of styrene by all the three complexes using PhIO and NaOCl as oxidant have been studied. The order of both the styrene conversion and styrene epoxidation using the three title compounds is 3 > 1 > 2. Again, it has been observed that more efficient conversion and epoxidation take place when PhIO is used as oxidant.  相似文献   

2.
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   

3.
The novel tridentate chiral ligand 2,6-bis{[(1R,2S,4R)-2-hydroxy-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-yl]}pyridine (1) was readily prepared by reaction of 2,6-dilithiopyridine with (R)-(−)-fenchone. Reaction of 1 with [MoO2(acac)2] resulted in the formation of the new metal-oxo five-coordinated complex [MoO2(ONO)] (2) [ONO = (1 – 2H)]. The reactivity of 2 has been studied and the derivatives [MoS2(ONO)] (3) and [MoO(O2)(ONO)] (4) were prepared. The compounds 14 have been characterised by 1H and 13C{1H} NMR, microanalysis and IR spectroscopy. Furthermore, the molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction. The behaviour of 2 as catalyst in oxotransfer and in nucleophilic substitution of propargylic alcohols reactions has been tested.  相似文献   

4.
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   

5.
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   

6.
Based on the versatile ligand 1H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (3,4′-Hbpt) (1), a series of coordination compounds [Ni(3,4′-Hbpt)(ip)] (2), [Ni(3,4′-Hbpt)2(tp)(H2O)2] (3), [Ni2(3,4′-Hbpt)(5-NO2-ip)2(H2O)4] (4) and [Ni(3,4′-Hbpt)(pm)0.5(H2O)3]·2H2O (5) have been hydrothermally constructed through R-phenyldicarboxyl (R = H, NO2 and COOH) intervention effect (ip = isophthalic anion, tp = terephthalic anion, 5-NO2-ip = 5-NO2-isophthalic anion, pm = pyromellitic anion). Structural analysis reveals that 3,4′-Hbpt adopts μ-Npy, Npy coordination modes in two typical conformations in these target coordination compounds. In cooperation with the auxiliary ligands benzenedicarboxylate connectors, a variety of Ni(II) coordination networks such as 2-D layer with (4, 4) topology (2) 1-D chain (3), honeycomb (4) and 2-D helical chains (5) have been assembled. Theoretical calculation based on density functional theory (DFT) for ligand (1) is also employed to explicate the stability of the different conformations. Moreover, thermal stability of these crystalline materials is explored by TG-DTG.  相似文献   

7.
Reactions of metal acetates with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) and co-ligands gave rise to four new complexes, namely [Zn2(3-abpt)(beta)(DMF) (H2O)2]n·nH2O (1), [Zn(3-abpt)(ip)]n·3nH2O (2), [Zn(3-abpt)(ip)(H2O)2]n·2nH2O (3), and [Cu2(3-abpt)2(C6H5COO)4(H2O)2]n·2nH2O (4) (ip = isophthalate, beta = 1,2,4,5-benzenetetracarboxylate). Compound 1 is a 3D coordination polymer with uncommon 3,4-connected (62.8)2(62.82.102) network. Compounds 24 are all 1D coordination polymers, which exhibit diversity structures. Compound 2 is a tubular-like chain, 3 is a ring-like network, and 4 is a zigzag chain. Their thermal stabilities and the photoluminescence of 1 have also been investigated.  相似文献   

8.
Three new copper complexes and one cobalt complex with 5-(pyrazinyl)tetrazolate anion, (pyztz), as chelating bidentate ligand, were obtained by the reaction of pyrazinecarbonitrile with sodium azide in the presence of copper(II) nitrate or cobalt(II)chloride. Complexes of composition [Cu(pyztz)2(H2O)] (1) deep blue crystals, [Cu(pyztz)2(H2O)2] (2a) green crystals, [Co(pyztz)2(H2O)2] (2b) orange crystals, [Cu(pyztz)2(H2O)2] · (H2O) (3) blue crystals were obtained. The single crystal X-ray diffraction revealed that complex 1 has square pyramidal structure with one water molecule at apical and two pyrazine-tetrazolato ligands at basal sites, while structures of 2a, 2b and 3 consist of octahedrally coordinated metal ions, where two pyztz anions act as bidentate ligands via one of the pyrazine-N atoms and one of the tetrazole-N atoms in trans-positions and two trans water molecules. Complex 3 contains one extra lattice water molecule. Hydrogen bonds of the types O–H?O and O–H?N connect the mononuclear units to a three-dimensional network structure in 2 (a and b are isostructural) and 3. Although the H-bond patterns look complex it is shown that they can be related to the well-known three- and six-connected rutile net (rtl) in 2 and the four- and six-connected fsh-net in 3.  相似文献   

9.
[MnCl2(NOR)(H2O)2] (1), [MnCl2(SPAR)(H2O)2] (2), [CoCl2(NOR)(H2O)2] (3) [CoCl2(SPAR)(H2O)2] (4), [CuCl2(phen)(NOR)] (5) and [CuCl2(phen)(SPAR)] (6) complexes with norfloxacin (NOR) and sparfloxacin (SPAR) were obtained from MnCl2·4H2O, CoCl2·4H2O and CuCl2(phen). In all cases the NOR and SPAR coordinate in the neutral zwitterionic form. The electron paramagnetic resonance spectra of the Cu(II) complexes (5) and (6) in aqueous and DMSO solutions indicate mixture of mononuclear and binuclear complex. Complexes (1-6), together with the corresponding ligands were evaluated for their in vitro trypanocidal effect, against both bloodstream trypomastigotes and intracellular forms of Trypanosoma cruzi. SPAR and NOR were poorly effective upon T. cruzi, complexes (3) and (4) were active against intracellular forms of the parasite. The complexes (5) and (6) displayed a higher activity upon both bloodstream and intracellular forms. The potency of fluoroquinolones, specially those coordinated to Cu(II)-phen justify further trypanocidal screening assays with this compounds in vitro as well as upon experimental models of T. cruzi infection.  相似文献   

10.
Four new nickel(II) phthalate compounds: mononuclear complexes [Ni(Im)]6(Pht)·H2O (1), [Ni(Pht)(Im)3(H2O)2]·H2O (2) and [Ni(Pht)(2-MeIm)3(H2O)3]·H2O (3), and coordination polymer [Ni(Pht)(4-MeIm)2(H2O)]n (4) (where Pht = dianion of o-phthalic acid, Im = imidazole, 2-MeIm = 2-methylimidazole, 4-MeIm = 4-methylimidazole) have been synthesized. The complexes 14 were characterised by elemental analysis, IR data, thermogravimetric, and X-ray diffraction analyses. X-ray analysis shows that the asymmetric unit of 1 consists of [Ni(Im)]62+ cation, Pht2− anion and solvate H2O molecule. The phthalate dianion does not take part in coordination to metal ion. The cations, anions and water molecules are linked via   N–H??O and O–H??O interactions forming 2D hydrogen-bonded networks. The structures of 2 and 3 are similar to other mononuclear Ni(II) phthalate complexes where Pht2− anions act as monodentate ligands and uncoordinated carboxylate oxygen atoms participate in the formation of hydrogen bonded double-chains. The structure of 4 consists of [Ni(4-MeIm)2(H2O)] building units connected by phthalate ions to form helical chains. The complexes 14 were tested for their ability to increase the biosynthesis of enzymes.  相似文献   

11.
The reactivity of (3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphine (L) hybrid ligand against Cu(I), Ag(I) and Au(I) has been assayed and compounds [Cu(L)2](PF6) (1), [Ag(L)]2(PF6)2·2C2H4Cl2·2C4H10O (2) and [AuCl(L)]2 (3) have been isolated and fully characterised. A fully characterisation by analytical and spectroscopic methods of 1-3 are presented and X-ray crystal structures of 1 and 2 are also reported. The similar data obtained between 2 and 3 permits to do a serious purpose of the structure of 3 in solid and solution.  相似文献   

12.
Two luminescent Pb(II) coordination frameworks containing dinuclear lead(II) units, [Pb(PYDC)(H2O)]n (1) and [Pb(HPHT)]n (2) have been prepared by the self-assembly of lead(II) salts with pyridinecarboxylate and benzenecarboxylate. Single-crystal X-ray diffraction analyses reveal that compound 1 is a three-dimensional architecture consisting of Pb2O2 dimeric building units, whereas compound 2 is a two-dimensional layer structure containing one-dimensional lead-oxide chains. The luminescent properties of 1 and 2 have been investigated in the solid state at room temperature, indicating structure-dependent photoluminescent properties of the coordination frameworks.  相似文献   

13.
Based on the versatile ligand 3,5-bis(4-pyridyl)-1H-1,2,4-triazole (Hbpt) derived from an in situ metal/ligand reaction, a series of coordination compounds CoCl4(H3bpt)(H2O) (1), Cu(H2bpt)2(SO4)2(H2O)6 (2), [Ag(bpt)]n (3), [Co(Hbpt)(pa)]n (4), [Co(Hbpt)(pda)]n (5) and [Cu(Hbpt)(pda)(H2O)]n (6) have been constructed (pa = phthalate, pda = 1,3-phenylenediacetate). The structures of these targeted complexes have been characterized by X-ray single-crystal diffraction techniques. Structural analysis reveals that Hbpt adopts versatile coordination modes to arrange the metal ions in 0-D point, simple (4,4) layers and dinuclear core chains in 13, which are further extended via the benzenedicarboxylate connectors to give rise to a variety of coordination networks such as (4,4), (412 · 63), (64 · 82) topologies in 46. The supramolecular organization through hydrogen bonds is analyzed for these complexes and thermal stability of these crystalline materials has been explored by TG-DTG.  相似文献   

14.
The bi-functional carbamoyl methyl pyrazole ligands, C5H7N2CH2CONBu2 (L1), C5H7N2CH2CONiBu2 (L2), C3H3N2CH2CONBu2 (L3), C3H3N2CH2CONiBu2 (L4) and C5H7N2CH2CON(C8H17)2 (L5) were synthesized and characterized by spectroscopic and elemental analysis methods. The selected coordination chemistry of L1 to L4 with [UO2(NO3)2 · 6H2O], [La(NO3)3 · 6H2O] and [Ce(NO3)3 · 6H2O] has been evaluated. Structures for the compounds [UO2(NO3)2 C5H7N2CH2CONBu2] (6) [UO2(NO3)2 C5H7N2CH2CONiBu2] (7) and [Ce(NO3)3{C3H3N2CH2CONiBu2}2] (11) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of the ligand L5 with U(VI) and Pu(IV) in tracer level showed an appreciable extraction for U(VI) and Pu(IV) up to 10 M HNO3 but not for Am(III). Thermal studies of the compounds 6 and 7 in air revealed that the ligands can be destroyed completely on incineration.  相似文献   

15.
A bioinorganic approach into the problem of the isomorphous substitution of calcium(II) by lanthanide(III) ions in biological systems is discussed. Reactions of malonamic acid (H2malm) with CaII and NdIII sources under similar conditions yielded the compounds [Ca(Hmalm)2]n (1), [Nd(Hmalm)2(H2O)2]n(NO3)n (2) and [Nd(Hmalm)2(H2O)2]nCln·2nH2O (3·2nH2O). Their X-ray crystal structure data show that the malonamate(-1) ligand presents two different ligation modes and coordinates through the two carboxylate and the amide-O atoms, thus bridging three CaII ions in 1 and two NdIII ions in 2 and 3·2nH2O. Complex 1 is a 3D coordination polymer based on neutral repeating units, whereas 2 and 3·2nH2O are 1D coordination polymers based on the same cationic repeating unit. Hydrogen bonding interactions further stabilize the 3D framework structure of 1 and assemble the 1D chains of 2 and 3·2nH2O into 3D networks. The three complexes were characterized spectroscopically (IR, far-IR, and Raman) and the thermal decomposition of 2 and 3·2nH2O was monitored by TG/DTA and TG/DTG measurements. Variable-temperature magnetic susceptibility data for 2 are also reported. The bioinorganic chemistry relevance of our results is discussed.  相似文献   

16.
The new cobalt (l) acyl compounds, [Co(PMe3)(CO)3(COMe)] 1, [Co(PPhMe2)(CO)3(COMe)] 2, [Co(P(4-Me-C6H4)3)(CO)3(COMe)] 3 and [Co(P(4-F-C6H4)3)(CO)3(COMe)] 4, have been prepared from [Na(Co(CO)4)]. The compound [Co(PCy3)(CO)3(COMe)] 5 has been prepared from [Co(PCy3)(CO)3(Me)] 6. The crystal structures of 5 and 6 are reported.  相似文献   

17.
The crystal structures of two pentacyanido(L) ferrate(III) complexes, [P(C6H5)4]2[Fe(CN)5(prz)]·4H2O 1, [P(C6H5)4]2[Fe(CN)5(4,4′-bipy)]·3H2O 2, have been solved. Within the two complex anions the iron atoms are hexacoordinated by five cyanido ligands, the sixth position being occupied by the nitrogen atom arising from pyrazine and, respectively, 4,4′-bipyridine. The electrochemical properties of compounds 1, 2 and of the azido derivative, (Ph4As)2[Na(H2O)4][Fe(CN)5(N3)] 3, have been investigated by cyclic voltammetry. A relatively complicated redox behavior of these complexes was found, due especially to the electron transfer involving the central metallic ion that changes reversibly its oxidation state (FeIII/FeII redox site) and also to the coligand (4,4′-bipyridine, pyrazine or azide) which intervenes in a distinct electron transfer. The experimental data have been rationalized through DFT calculations.  相似文献   

18.
The compounds [MoCl(NAr)2R] (R=CH2CMe2Ph (1) or CH2CMe3(2); Ar=2,6-Pri2C6H3) have been prepared from [MoCl2(NAr)2(dme)] (dme=1,2-dimethoxyethane) and one equivalent of the respective Grignard reagent RMgCl in diethyl ether. Similarly, the mixed-imido complex [MoCl2(NAr)(NBut)(dme)] affords [MoCl(NAr)(NBut)(CH2CMe2Ph)] (3). Chloride substitution reactions of 1 with the appropriate lithium reagents afford the compounds [MoCp(NAr)2(CH2CMe2Ph)] (4) (Cp=cyclopentadienyl), [MoInd(NAr)2(CH2CMe2Ph)] (5) (Ind=Indenyl), [Mo(OBut)(NAr)2(CH2CMe 2Ph)] (6), [MoMe(NAr)2(CH2CMe2Ph)] (7), [MoMe(PMe3)(NAr)2(CH2CMe 2Ph)] (8) (formed in the presence of PMe3) and [Mo(NHAr)(NAr)2(CH2CMe2P h)](9). In the latter case, a by-product {[Mo(NAr)2(CH2CMe2Ph) ]2(μ-O)}(10) has also been isolated. The crystal structures of 1, 4, 5 and 10 have been determined. All possess distorted tetrahedral metal centres with cis near-linear arylimido ligands; in each case (except 5, for which the evidence is unclear) there are α-agostic interactions present.  相似文献   

19.
The reactions of 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine with CuCl2 · 2H2O, Cu(NO3)2 · 3H2O and CuSO4 · 5H2O have been examined, and four [CuCl2(dppt)] (1), [CuCl2(dppt)2] · 2MeOH (2), [Cu(dppt)2(H2O)2](NO3)2 (3) and [Cu(SO4)(dppt)(H2O)]n · nH2O (4) complexes have been obtained. All the complexes have been structurally and spectroscopically characterized, and compound 4 has been additionally studied by magnetic measurements. The electronic structure of 1 has been calculated with the density functional theory (DFT) method, and the time-dependent DFT calculations have been employed to calculate the electronic spectrum of 1.  相似文献   

20.
Five novel heterobimetallic compounds [Cu(bpzm)2Hg(SCN)4]n (1), [Cu(bdmpzm)2(μ-SCN)Hg(SCN)3] (2), [Cu(pybzim)2(μ-SCN)Hg(SCN)3]·H2O (3), [Cu(bipy)2(μ-SCN)Hg(SCN)3][Cu(bipy)2(μ-SCN)2Hg(SCN)2] (4) and [Cu(bipy)(NCS)]2[Hg(SCN)4] (5) have been synthesized and structurally characterized (bpzm-bis(pyrazol-1-yl)methane, bdmpzm-bis(3,5-dimethylpyrazol-1-yl)methane, pybzim-2-(2-pyridyl)benzimidazole, phen-1,10-phenantroline and bipy-2,2′-bipyridine). The compounds 2, 3, 4 and 5 are molecular complexes, whereas 1 is an alternating 1-D zigzag chain of [Cu(bpzm)2]2+ and Hg(SCN)4]2− moieties in which the metal atoms are bridged via thiocyanate ions. The polymer 1 has been studied by magnetic measurement.  相似文献   

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