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1.
The extraction of U(VI) with 1-phenyl 2,3 dimethyl-5-pyrazolone, at a pH of 2.5, in the presence of common anions, like perchlorate and tri-, di-, and monochloroacetates has been investigated. The optimum experimental conditions have been evaluated by studying various parameters such as pH, equilibration period, reagent concentration, metal concentration, and solvents. Effect of diverse anions and cations on the extraction has also been studied. The extracted species, determined by log D - log R plots are represented as, [UO2(Apy)4(ClO4)2], [UO2(Apy)2(TCA)2], [UO2(Apy)2(DCA)2], [UO2(Apy)(H2O)(MCA)2]. The conditional stability constants of the quantitatively extracted complexes are calculated. The proposed method allows the selective separation of uranium(VI) from multicomponent mixtures and geological matrices and is also applied for the separation and chemical characterization of impurities at trace and ultratrace levels.  相似文献   

2.
Summary Reaction of 1,4,8, 12-tetra-azacyclopentadecance ([15])-aneN4) with an excess of acrylonitrile gives theN-tetracyanoethylated ligand (L). Several new complexes of this ligand with nickel(II), copper(II) and zinc(II) have been prepared and characterised. The complexes can be formulated [NiL]n(ClO4)2n, [ML](ClO4)2 (M=CuII and ZnII), [NiL(NCS)2], [NiLCl2], [CuL](NO3)2 and [NiL]n(NO3)2n·2H2O. Spectral, magnetic and conductivity data are reported and possible structures are considered.  相似文献   

3.
By reacting [Pd( )(μ-Cl)]2 with AgClO4 in NCMe, the corresponding cationic complexes [Pd( )(NCMe)2]ClO4 ( = phenylazophenyl-C2,N1; dimethylbenzylamine-C2,N; 8-methylquinoline-C8,N) can be obtained. Solutions containing the cations [Pd( )(S)2]+ are obtained when the reaction is carried out in tetrahydrofuran or acetone (S). The treatment of these solutions with bidentate ligands (L—L) (Ph2PCH2PPh2,Ph2PNHPPh2 or Ph2PCH2PPh2CHC(O)Ph) gives the mononuclear [Pd( )(L3l)]ClO4 complexes, with L3l acting as a chelate ligand. On the other hand [Pd( (μ-Cl)]2 reacts with L3l (Ph2PCH2PPh2, Ph2PNHPPh2) yielding [Pd( )Cl(L3l)] with L3l acting as monodentate. The reactions between [Pd( )(NCMe)2]ClO4 and 2,2′-bipyrimidyl give rise to the formation of the mononuclear [Pd( ) (bipym)]ClO4 or binuclear [Pd2( )2(μ-bipym)](ClO4)2, [( )Pd(μ-bipym)Pd( )](ClO4)2 derivatives. Finally [Pd( )Cldppm] (dppm = Ph2PCH2PPh2) react with NaH producing the neutral complexes [Pd( )(ddppm)] (ddppm = Ph2PCHPPh2) which by reaction with HCl lead again to the starting materials [Pd( )Cl(dppm)].  相似文献   

4.
Synthetic procedures are described that allow access to the new complexes cis-[Mo2O5(apc)2], cis-[WO2(apc)2], trans-[UO2(apc)2], [Ru(apc)2(H2O)2], [Ru(PPh3)2(apc)2], [Rh(apc)3], [Rh(PPh3)2(apc)2]ClO4, [M(apc)2], [M(PPh3)2(apc)]Cl, [M(bpy)(apc)]Cl (M(II) = Pd, Pt), [Pd(bpy)(apc)Cl], [Ag(apc)(H2O)2] and [Ir(bpy)(Hapc)2]Cl3, where Hapc, is 3-aminopyrazine-2-carboxylic acid. These complexes were characterized by physico-chemical and spectroscopic techniques. Both Hapc and several of its complexes display significant anticancer activity against Ehrlich ascites tumour cells (EAC) in albino mice.  相似文献   

5.
The synthesis and properties of neutral and cationic complexes of general formulae [{RhCl(diolefin)}2(CH2(pz)2)], [Rh(CO)2 (CH2(pz)2)][RhCl2(CO)2], (Rh(diolefin)(CH2(pz)2)]ClO2, [{Rh(diolefin)(PPh3)}2(CH2(pz)2)](ClO4)2, [Rh(CO)2(CH2(pz)2)]ClO4 and [Rh(CO)(CH2(pz)2)(PPh3)]ClO4 are described. The NMR spectra of [Rh(COD)(CH2(pz)2)]ClO4 complexes are discussed. X-ray structural analysis of [Rh(COD)(CH2(Pz)2)]ClO4 · 12C2H4Cl2 is presented; the final R factor is 0.061 for 2436 observed data, recorded with Cu-Kα, not corrected for absorption and with the sample inside a capillary. The Rh atom presents a distorted square planar coordination in a mononuclear arrangement. The COD ring has a twisted boat conformation, and the two halves of the CH2(Pz)2 moiety, which are quite similar to one another, form an angle of 47.2(4)°.  相似文献   

6.
Polypyridyl ruthenium(II) complexes [RuII(3-bptpy)(dmphen)Cl]ClO4 (1), [RuII(3-cptpy)(dmphen)Cl]ClO4 (2), [RuII(2-tptpy)(dmphen)Cl]ClO4 (3), and [RuII(9-atpy)(dmphen)Cl]ClO4 (4) {where 3-bptpy?=?4′-(3-bromophenyl)-2,2′:6′,2″-terpyridine, 3-cptpy?=?4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine, 2-tptpy?=?4′-(2-thiophenyl)-2,2′:6′,2″-terpyridine, 9-atpy?=?4′-(9-anthryl)-2,2′:6′,2″-terpyridine, dmphen?=?2,9-dimethyl-1,10-phenanthroline} have been synthesized and characterized. The DNA-binding properties of the complexes with Herring Sperm DNA have been investigated by absorption titration and viscosity measurements. The ability of complexes to break the pUC19 DNA has been checked by gel electrophoresis. The experimental results suggest that all the complexes bind DNA via partial intercalation. The results also show that the order of DNA-binding affinities of the complexes is 4?<?3?<?2?<?1, confirming that planarity of the ligand in a complex is very important for DNA-binding.  相似文献   

7.
The reactions of AuIII, PtII and PdII complexes with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic (H2O, MeOH, EtOH) and aprotic (DMF, CH2Cl2) solvents. Compounds in which the pyridine ligand is N-coordinated, either in the original aldehydic form or in a new form derived from addition of one or two protic molecules, have been isolated, namely: [Au(2CHO-py · H2O)Cl3], [Au(2CHO-py · MeOH)Cl3], [Au(2CHO-py · 2EtOH)Cl3], cis-[Pt(2CHO-py)2Cl2], trans-[Pd(2CHO-py)2Cl2], trans-[Pt(dmso)(2CHO-py)Cl2], [Pt{C5H4N-(CH2SMe)}Cl(2CHO-py)](ClO4), [Pt(terpy)(2CHOpy)](ClO4)2, [Pt(terpy)(2CHO-py · H2O)](ClO4)2 (terpy = 2,2′:6′,2′′-terpyridine). 1H-n.m.r. experiments show that the addition of the protic molecule(s) to the PtII and PdII complexes is reversible. The effects of the nature of the metal ion and the ancillary ligands as well as of the total charge of the complexes on the relative stability of the addition products are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

8.
Four new complexes of UO2(II) and Th(IV) with bis-Schiff bases, derived from N,N'-bis[(l-phenyl-3-methyl-5-oxo-4-pyrazolinyl)-a-furylmethylidyne]-1,2-propylenediimine [1,2-BPMOPFP-H2] and N,N'- bis[(l-phenyl-3-methyl-5-oxo-4-pyrazolinyl)-a-furylmethylidyne]-1,3-propylenediimine [1,3-BPMOPFP-H2], were synthesized and characterized by elemental analysis, IR, UV, 1HNMR spectroscopy, and molar conductivity. The general formula of the complexes was confirmed to be [UO2(BPMOPFP)], [Th(BPMOPFP)(NO3)]NO3. A possible structure for the complexes have been proposed.  相似文献   

9.
《Polyhedron》2005,24(16-17):2593-2598
Complexes [MnII(5bpno)3(ClO4)2], [MnII(5bpno)(CH3OH)2Cl2], [CuII(5bpno)2(ClO4)2], and [CuII(5bpno)Cl2] were prepared, where 5bpno stands for 2,2′-bipyridin-5-yl t-butyl nitroxide. X-ray crystallographic analysis clarified that the Cu ion in [Cu(5bpno)2(ClO4)2] was tetra-coordinate with four nitrogen atoms forming two chelate rings. Magnetic measurements revealed the presence of ferromagnetic couplings in the Mn complexes, whereas the Cu complexes showed antiferromagnetic couplings. Magnetic exchange couplings between the metal and radical spins through the intervening pyridine ring can be explained in terms of the spin-polarization mechanism.  相似文献   

10.
《印度化学会志》2021,98(11):100182
The reaction of (Z)-2-(phenyl(2-(pyridin-2-yl)hydrazono)methyl)pyridine (L) and copper(II) salt in methanol yields a series of five pentacoordinated mononuclear complexes. The molecular formulations of these complexes are as [Cu(L)(ImH)2](ClO4)2 (1), [Cu(L)(2-MeImH)2](ClO4)2 (2), [Cu(L)(2-EthImH)2](ClO4)2 (3), [Cu(L)(BenzImH)2](ClO4)2 (4) and [Cu(L)(2-MeBenzImH)2](ClO4)2 (5) (where ImH ​= ​Imidazole, 2-MeImH ​= ​2-Methylimidazole, 2-EthImH ​= ​2-Ethylimidazole, BenzImH ​= ​Benzimidazole, 2-MeBenzImH ​= ​2-Methylbenzimidazole). The room temperature magnetic moment values are in the range 1.79–1.81 B ​M. The conductance measurements suggest that they are electrolytic in nature. The DFT calculations were performed to get information about the structures of the complexes. The copper(II) centre in all complexes is a Penta-coordinated. The proligand has NNN donor sites viz., two pyridine N and one azomethine N atoms, whereas co-ligand coordinates through pyridine N atom forming two five-membered chelate rings. The τ5 values of these complexes are in the range 0.177–0.495. Both pro and co-ligands are neutral. X-band Epr spectral measurements have been carried out to authenticate the paramagnetic behaviours of all complexes. The stability of the copper(II) centre was examined using cyclic and differential pulse Voltammetry. The IC50 and SOD activity values for all complexes reveal that they are good SOD active complexes. The IC50 value of present complexes remains in the range 26–43 ​μM.  相似文献   

11.
Ni(II) di(pentyl)dithiocarbamates of composition [Ni(Pe2dtc)2], [NiX(Pe2dtc)(PPh3)] (X = Cl, Br, I, NCS), [Ni(NCS)(Pe2dtc)(PBut3)], [Ni(Pe2dtc)(PPh3)2]ClO4 and [Ni(Pe2dtc)(PPh3)2]PF6 (Pe2dtc = di(pentyl)dithio-carbamate, PPh3 = triphenylphosphine, PBut3 = tributylphosphine) have been synthesized. The complexes have been characterized by the usual methods. X-ray structure analyses confirmed the nature of [NiI(Pe2dtc)(PPh3)] and [Ni(Pe2dtc)(PPh3)2]ClO4 complexes.  相似文献   

12.
The complexes fac-O3ClOMn(CO)3(NN) (NN = 1,10-phenantroline (phen) or 2,2'bipyridine (bipy)) react with an excess of the ligands L [L = P(OR)3 or P(OR)2Ph, R = Me or Et] in refluxing ethanol to give cis-trans-[Mn(CO)2-(NN)L2]ClO4, or the more highly substituted [Mn(CO)(NN)L3]ClO4 if the reaction is carried out under UV irradiation. Carbonylation at normal pressure of the latter complexes results in the formation of cis-cis-[Mn(CO)2(NN)L2]ClO4, which undergo isomerization to the cis-trans isomer when heated in acetone.Treatment of fac-O3ClOMn(CO)3(dpe) (dpe = 1,2-bis(diphenylphosphino)-ethane] with bipy or phen in refluxing ethanol gives the corresponding cis-[Mn(CO)2(NN)(dpe)]ClO4 complexes, and irradiation of these with UV in the presence of an excess of P(OR)3 (R = Ph, Et or Me) gives the monocarbonyls [Mn(CO)(NN)(dpe)L]ClO4.  相似文献   

13.

Abstract  

Three copper(II), one zinc(II), and one ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different metal/ligand molar ratios, formulated as [Cu(3-bromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (1), [Cu(3,8-dibromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (2), [Cu(3,8-dibromo-phen)(ClO4)(H2O)3](ClO4)(H2O)3 (3), [Zn(3,8-dibromo-phen)2(H2O)2](ClO4)2(H2O)2 (4), and [Fe(3,8-dibromo-phen)3](ClO4)2(H2O)(CH4O)(C3H6O)2 (5) (phen = 1,10-phenanthroline), have been synthesized and characterized in this paper. X-ray single-crystal diffraction studies reveal the different crystallographic symmetry and packing fashions between neighboring phen rings in 1:1 Cu(II) complexes 13 due to the alteration of bromo substituent 1,10-phenanthroline ligands and coordinated or free solvent molecules. Additionally, in 1:2 Zn(II) and 1:3 Fe(II) complexes 4 and 5, continuous π–π stacking and alternating π–π and dimeric p–π stacking are found.  相似文献   

14.
Summary New coordination compounds of NiII and CoII with dichloropyrimidinoguanidine (L) have been obtained and characterized by physico-chemical and spectroscopic methods. The complexes have the general formulae: [ML3](ClO4)2, [ML2(SO4)], [ML2(NCS)2], (M = Ni or Co), [NiL2(ClO4)2] and [CoL2](ClO4)2. The ligands are bonded to the metal ion via one nitrogen atom from the pyrimidine heterocyclic ring and one from the guanidine group.  相似文献   

15.
Several Cu(II) complexes with 1,2,4-triazolo[1,5-a]pyrimidine (tp) and its 5,7-dimethyl derivative (dmtp) have been isolated and structurally characterized. Five of them are mononuclear and contain 1,10-phenanthroline (phen) or ethylenediamine (en) as auxiliary ligands, their formula being [Cu(H2O)(phen)(tp)2](ClO4)2 · H2O, [Cu(H2O)(phen)(dmtp)2](ClO4)2, [Cu(NO3)(H2O)(phen)(tp)](NO3), [Cu(H2O)2(en)(tp)2](ClO4)2 and [Cu(H2O)2(en)(dmtp)2](ClO4)2. In all these compounds the tp or dmtp ligand is monodentately coordinated via the nitrogen atom in position 3. The auxiliary ligand influences the coordination number, which is five when this ligand is phen and six when it is en whereas the number of triazolopyrimidine ligands linked to the metal seems to be influenced by the nature of the counteranion. A dinuclear compound with tp has also been isolated, its formula being [Cu2(OH)(H2O)2.5(tp)5](ClO4)3·(H2O)1.5, with both metal atoms linked by an hydroxydo group and by a tp bridging ligand, coordinated to one of the copper atoms via N3 and to the other via N4. This compound has several unusual features among the metal complexes with triazolopyrimidine derivatives: the presence of two different kinds of bridging moieties, the coexistence of bridging and terminal ligands and the formation of a N3–N4 bridge for a Cu(II) dinuclear compound for a derivative without exocyclic oxygen atoms.  相似文献   

16.
Reduction by NaBH4 of the imine functions of (5,7,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)-nickel(II) and -copper(II), and of their 13-ethyl-5,7,7-trimethyl-homologues, yield the nitro-substituted cyclic tetraamine cations (5,5,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradecane)-nickel(II) and -copper(II), [M(neh)]2+, and (13-ethyl-5,5,7-trimethyl-homologues, [M(nph)]2+, respectively. The nickel(II) cations form square–planar, singlet ground, state salts with poorly coordinating anions and octahedral, triplet ground state, compounds with additional ligands, trans-β-[Ni(neh)A2], A = Cl, NCS and trans-β-[Ni(neh)A2](ClO4)2, X = NH3, MeCN, all with nitrogen configuration III, 1R,4R,8S,11S = β. With oxalate the chain-polymeric compound catena-trans-β-[Ni(neh)(μ-C2O4)]n · 3n(H2O) is formed. Folded macrocycle compounds cis-α-[Ni(neh)(C5H7O2)]ClO4 and cis-α-[{Ni(neh)}2(C2O4)](ClO4)2 are formed with the chelates acetylacetonate and oxalate, with configuration 1R,4R,8R,11R = α. These react with HClO4 to form metastable α-[Ni(neh)](ClO4)2 with retention of configuration. The copper(II) cations form crimson salts with poorly coordinating anions and compounds of the type β-[Cu(neh)A]ClO4 of varying shades of blue with coordinating anions. Structures of singlet ground state square–planar nickel(II) compounds β-[Ni(neh)](ClO4)2 · H2O, β-[Ni(neh)](ClO4)2, β-[Ni(neh)]2[ZnCl3(OH2)]2[ZnCl4] · H2O and α-[Ni(neh)](ClO4)2, the triplet ground state chain-polymeric compound catena-trans-β-[Ni(neh)(μ-C2O4)]n · 3n(H2O) and of square–pyramidal β-[Cu(nph)Cl]ClO4 are reported.  相似文献   

17.
Reaction of 1-(2′-pyridylazo)-2-naphthol (Hpan) with [Ru(dmso)4Cl2] (dmso = dimethylsulfoxide), [Ru(trpy)Cl3] (trpy = 2,2′,2″-terpyridine), [Ru(bpy)Cl3] (bpy = 2,2′-bipyridine) and [Ru(PPh3)3Cl2] in refluxing ethanol in the presence of a base (NEt3) affords, respectively, the [Ru(pan)2], [Ru(trpy)(pan)]+ (isolated as perchlorate salt), [Ru(bpy)(pan)Cl] and [Ru(PPh3)2(pan)Cl] complexes. Structures of these four complexes have been determined by X-ray crystallography. In each of these complexes, the pan ligand is coordinated to the metal center as a monoanionic tridentate N,N,O-donor. Reaction of the [Ru(bpy)(pan)Cl] complex with pyridine (py) and 4-picoline (pic) in the presence of silver ion has yielded the [Ru(bpy)(pan)(py)]+ and [Ru(bpy)(pan)(pic)]+ complexes (isolated as perchlorate salts), respectively. All the complexes are diamagnetic (low-spin d6, S = 0) and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a Ru(II)–Ru(III) oxidation on the positive side of SCE. Except in the [Ru(pan)2] complex, a second oxidative response has been observed in the other five complexes. Reductions of the coordinated ligands have also been observed on the negative side of SCE. The [Ru(trpy)(pan)]ClO4, [Ru(bpy)(pan)(py)]ClO4 and [Ru(bpy)(pan)(pic)]ClO4 complexes have been observed to bind to DNA, but they have not been able to cleave super-coiled DNA on UV irradiation.  相似文献   

18.
Summary Studies on the chelates of cobalt(II) with the bidentate ligands 1,4-diphenyl(2,3-dimethyl-1,4-diazabutadiene) (PMB) and 1,4-di(p-methoxyphenyl)-2,3-dimethyl-1,4-diazabutadiene (MPMB) have been carried out. On the basis of elemental analyses, the complexes are [Co(PMB)Cl2], [Co(PMB)2(C1O4)2], [Co(MPMB)Cl2] and [Co(MPMB)2(ClO4)2].Both ligands are bidentatevia nitrogen atoms in all the complexes. The magnetic susceptibility and i.r. and u.v.-visible spectra are reported and discussed. The chloro-compounds involving two chlorine ligands and, in the perchlorate compounds, the ClO 4 groups are bound to the cobalt(II) centre.  相似文献   

19.
Summary A new tri-cavity decaaza macrocycle (TCM) has been synthesised by the condensation of tetra(aminopropyl)-cyclam with diethanolamine. The new macrocyclic ligand forms tri-nuclear complexes, [Cu3(TCM)(H2O)2]-(ClO4)6 and [Ni3(TCM)(H2O)2](ClO4)6.  相似文献   

20.
The extraction behavior of Th(IV) from dilute nitric as well as perchloric acid medium using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and its mixture with tri-n-octyl phosphine oxide (TOPO) was investigated. The species of the type Th(X)(PMBP)3·(HPMBP) and Th(X)(PMBP)3·(TOPO) were extracted for the binary and ternary extraction systems, respectively, where X=NO3− or ClO4−. The presence of 1.25·10−5M Th carrier in the aqueous phase resulted in the extracted species of the type of Th(PMBP)4 and Th(PMBP)4·(TOPO), respectively. The extraction constant (logk ex ) for the binary species Th(PMBP)4 was found to be 6.89±0.01 while the overall extraction constant (logK) for the ternary species Th(PMBP)4·(TOPO) was calculated to be 13.17±0.06.  相似文献   

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