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1.
Summary Reaction of 5,7-dioxo-1,4,8,11-tetra-azacyclotetradecane with acrylonitrile gives the dicyanoethylated ligand (L). The Cu II complex [CuLH -2]·2H 2O has been isolated from basic solution where the macrocycle is deprotonated and acts as a dinegative quadridentate ligand. The ligand L is protonated in acidic solution and the ionisation equilibria can be summarised as LH
inf2
sup2+
LH + +H +; K 1 LH + L + H +; K 2 where pK 1 = 3.05 and pK 2 = 5.94 at 25 °C and I = 0.1 mol dm -3 (NaNO 3). Complexation with Cu II can be represented by the equilibria at 25 °C. Cu 2+ + L [CuLH -1] + + H +; log 11 – 1 = -3.43 Cu 2+ + L [CuLH -2] + 2H 2+; log 11 – 2 = -9.18 For Ni II only the single equilibrium is of importance. Ni 2+ + L [NiLH -2] + 2H 2+; log 11 – 2 = -14.45 相似文献
2.
Reactions of diiron complexes (E)[ 5-t-BuC 5H 3)Fe(CO)] 2(-CO) 2 [E = Me 2Si (1), Me 2SiSiMe 2 (2), and Me 2SiOSiMe 2 (3)] with iodine in CHCl 3 yielded diiodide complexes (E)[ 5-t-BuC 5H 3)Fe(CO) 2I] 2 [E=Me 2Si (5), Me 2SiSiMe 2 (6), and Me 2SiOSiMe 2 (7)]. Like (1–3), complexes (5–7) also exists as mixtures of cis and trans isomers even though the Fe–Fe bond in (1–3) has been cleaved. When the pure isomers (1–3) reacted with iodine respectively in CHCl 3, the cis isomers (1c–3c) yielded only the cis products (5c–7c), whereas the trans isomers (1t–3t) yielded only the trans isomers (5t–7t). This indicates that iodination of bridged diiron complexes is stereospecific. Similar treatment of trans-(Me 2Si)[{ 5-t-(heptyl)C 5H 3}Fe(CO)] 2(-CO) 2 (4t) with iodine gave only the trans product (Me 2Si)[{ 5-t-(heptyl)C 5H 3}Fe(CO) 2I] 2 (8t). The molecular structure of (5t) was determined by X-ray diffraction. 相似文献
3.
Two coordination polymers, namely [M(cpna)(phen)(H 2O)]
n
(M = Ni, 1; Cd , 2, H 2cpna = 5-(2′-carboxylphenyl) nicotic acid, phen = 1,10-phenanthroline), have been hydrothermally synthesized and characterized
by single-crystal X-ray diffraction, magnetic and luminescence measurements. Single-crystal X-ray diffraction studies show
that the two complexes are isostructural polymers. They have 1D step-like chain structures, which are further extended into
3D metal–organic supramolecular frameworks by π–π stacking interactions. Magnetic studies for complex 1 show antiferromagnetic coupling between the adjacent Ni(II) centers, with g = 2.10 and J = −4.30 cm −1. Complex 2 displays strong green fluorescent emission at room temperature. 相似文献
4.
New complexes of type [M(HL)(CH 3COO)(OH 2) m]·nH 2O (where M:Co, m = 2, n = 2; M:Ni, m = 2, n = 1.5; M:Zn, m = 0, n = 2.5 and M:Cd, m = 0, n = 0; H 2L:5-bromo- N, N′-bis-(salicylidene)- o-tolidine) have been synthesized and characterized by microanalytical, IR, UV–Vis-NIR and magnetic data. Electronic spectra of Co(II) and Ni(II) complexes are characteristic for an octahedral stereochemistry. The IR spectra indicate a chelate coordination mode for mono-deprotonated Schiff base and a bidentate one for acetate ion. The thermal transformations are complex according to TG and DTA curves including dehydration, acetate decomposition and oxidative degradation of the Schiff base. The final product of decomposition is the most stable metallic oxide. 相似文献
5.
The synthesis of complexes of the general form M(dmdp)Cl 2, where dmdp is 6, 6′-dimethyl-2, 2′-dipyridyl and M is Pd(II), Pt(II), Cu(II), Co(II) and Zn(II) from non-aqueous solvents is reported. Also presented is a new convenient synthesis of dmdp. The characteristics of these complexes to produce nicks in the phosphodiester backbone of DNA are evaluated. 相似文献
6.
The infrared and Raman spectra of the ligands; 2-(α-hydroxybenzyl)thiaminium chloride (HBT), 2-(α-hydroxycyclohexylmethyl)thiaminium chloride (HCMT), and their protonated forms HBT·HCl and HCMT·HCl, as well as of their zwitterionic type complexes Zn(HBT)Cl 3, Cd(HBT)Cl 3, Hg(HBT)Cl 3 and Zn(HCMT)Cl 3, Cd(HCMT)Cl 3, Hg(HCMT)Cl 3, have been recorded in the region 4000-50 cm −. Several characteristic bands have been identified or tentatively assigned and are discussed in relation to the structures of the complexes. It is concluded from the spectra that the complexes are isostructural and that the bonding site of the ligands is the N(1′) atom of the pyrimidine moiety. 相似文献
7.
The complexes [Cd(H 2O) 6](C 5HN 2O 6) 2 · 2H 2O ( I) and [Co(H 2O) 6](C 5HN 2O 6) 2 · 2H 2O ( II) were obtained in the crystalline state by reactions of cobalt chloride and cadmium chloride with ammonium 4-nitro-2,3,5,6-tetraoxopyridinate, (NH 4) 2 · (C 5HO 6N 2) 2. Their cocrystallization gave the heterometallic complex [Cd 0.32Co 0.68(H 2O) 6](C 5HN 2O 6) 2 · 2H 2O ( III). The crystal and molecular structures of complexes I-III were determined by X-ray diffraction. It was demonstrated that the complexation reactions occur by replacement of two ammonium cations 4-nitro-2,3,5,6-tetraoxopyridinate by the complex cations [M(H 2O) 6] 2+. The tetraoxopyridinate anions and the complex cations are hydrogen-bonded through the coordinated and crystallization water molecules as well as through the O atoms of the organic anion. The thermolysis of complexes I and II was examined by TGA. 相似文献
8.
Three novel heterobinuclear complexes have been prepared and identified as [Cu(oxap)Ni(L) 2](ClO 4) 2·ξH 2O, where oxap denotes the N,N′-bis(2-aminopropyl)oxamido dianion and L denotes 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) or 5-nitro-1,10-phenanthroline
(NO 2-phen). The crystal structure of [Cu(oxap)Ni(phen) 2]-(ClO 4) 2·2H 2O has been determined. Crystal data: triclinic, space group
, a=12.079 (6), b=12.409 (4), c=17.261 (8) ?, α=70.91 (2), β=86.72 (4), γ=89.19 (3) o. At room temperature, Z=2. The Cu II is in a square planar environment and the Ni II is in an octahedral environment. The Cu−Ni distance is 5.292 ?. The temperature dependences of the magnetic susceptibilities
of [Cu(oxap)Ni(phen) 2]-(ClO 4) 2·2H 2O and [Cu(oxap)Ni(bipy) 2](ClO 4) 2 have been studied in the 4.2–300 K range, giving the exchange integral J=−92.4 cm −1 for bipy and J=−94.3 cm −1 for phen. These results are commensurate with antiferromagnetic interactions between the adjacent metal ions. 相似文献
9.
The coordination of 10-electron diatomic ligands (BF, CO N 2) to iron complexes Fe(CO) 2(CNAr Tripp2) 2 [Ar Tripp2=2,6-(2,4,6-( iso-propyl) 3C 6H 2) 2C 6H 3] have been realized in experiments very recently ( Science, 2019 , 363, 1203–1205). Herein, the stability, electronic structures, and bonding properties of (E 1E 2)Fe-(CO) 2(CNAr Tripp2) 2 (E 1E 2=BF, CO, N 2, CN −, NO +) were studied using density functional (DFT) calculations. The ground state of all those molecules is singlet and the calculated geometries are in excellent agreement with the experimental values. The natural bond orbital analysis revealed that Fe is negatively charged while E 1 possesses positive charges. By employing the energy decomposition analysis, the bonding nature of the E 2E 1–Fe(CO) 2(CNAr Tripp2) 2 bond was disclosed to be the classic dative bond E 2E 1→Fe(CO) 2(CNAr Tripp2) 2 rather than the electron-sharing double bond. More interestingly, the bonding strength between BF and Fe(CO) 2(CNAr Tripp2) 2 is much stronger than that between CO (or N 2) and Fe(CO) 2(CNAr Tripp2) 2, which is ascribed to the better σ-donation and π back-donations. However, the orbital interactions in CN −→Fe(CO) 2(CNAr Tripp2) 2 and NO +→Fe(CO) 2(CNAr Tripp2) 2 mainly come from σ-donation and π back-donation, respectively. The different contributions from σ donation and π donation for different ligands can be well explained by using the energy levels of E 1E 2 and Fe(CO) 2(CNAr Tripp2) 2 fragments. 相似文献
10.
By reaction of Me 3SiSBu with anhydrous tin(II) chloride bis(butylthio)tin was obtained that exemplified a coordination polymer [Sn(SBu) 2]
n
, whose elementary unit contained according to X-ray diffraction study three independent four-membered rings Sn 2S 2 of unusual geometry. It was demonstrated that polymeric thiolates [E(SBu) 2]
n
(E = Ge, Sn) readily reacted with TsiLi (Tsi = C(SiMe 3) 3) in a mixed solvent ether THF affording in a good yield ate-complexes [(Me 3Si) 3CE(-SBu) 2Li(THF) 2]. Both complexes contain a four-membered ring in a butterfly conformation where the lithium atom is symmetrically bonded to both sulfur atoms, and the coordination polyhedra of Ge and Sn atoms may be regarded as distorted tetrahedra AB 3X, where one of coordination places is occupied by unshared electron pair. The structure of the ate-complexes observed in a crystal is conserved also in solution of nonpolar solvents. 相似文献
11.
A new 1,2-diamine ligand, N, N-bis(2-hydroxyethyl)stilbenediamine (L), has been prepared by reduction of the condensation product of benzaldehyde with 2-aminoethanol with Al amalgam. Mononuclear complexes of the [CuL(H 2O)]X 2 type where X=Cl – or AcO – with Cu II and PdLCl 2 with palladium(II) have been prepared and characterized by elemental analysis and i.r., u.v.–vis. or 1H-n.m.r. spectroscopy. 相似文献
12.
A new vic-dioxime ligand containing 1,3-dioxolane ring and 1,4-diaminobutane, ( E, E)- N-hydroxy-2-(hydroxyimino)- N-(4-{[(2-phenyl-1,3-dioxolan-4-yl)methyl]amino}butyl)ethanimidamide (H 2L) and the metal mononuclear complexes with a 1 : 2 and 1 : 1 metal–ligand ratio have been prepared with chloride salts Co(II), Ni(II), Cu(II), and Zn(ll) in EtOH. The structures of the ligand and its complexes have been established by microanalyses, IR, UV-VIS, 1H and 13C NMR spectra, elemental analyses, and conductivity and magnetic susceptibility measurements. Also their thermal behavior has been studied by the TGA analysis. 相似文献
14.
Ohne Zusammenfassung 相似文献
15.
In this study, a mononuclear CuL complex was prepared by the use of bis-N,N′-(salicylidene)-1, 3-propanediamine (LH2) and Cu2+ ion. NiCl2 and NiBr2 salt were treated with this complex in dioxanewater medium and two new complexes [(CuL)2NiCl2(H2O)2] and [(CuL)2NiBr2(H2O)2)] with Cu(II)–Ni(II)–Cu(II) nucleus structure were obtained. In addition to this bis-N,N′-(2-hydroxybenzyl)-1,3-diaminopropane (LHH2) was prepared by the reduction of LH2 with NaBH4 in MeOH medium. The treatment of this reduced complex with Cu2+ ion resulted a complex [(CuLH)2CuCl2] with a structure of Cu(II)–Cu(II)–Cu(II). The complexes prepared were characterized by the use of elemental analysis, IR spectroscopy, thermogravimetric and X-ray diffraction methods. The crystal structures of [(CuL)2NiBr2(H2O)2] (СIF file CCDC 1448402) and [(CuLH)2CuCl2] (СIF file CCDC 1448401) complexes were elucidated. It was found that halogen ions are coordinated to terminal Cu2+ ions which are in a distorted square pyramid coordination sphere. It was determined that the central Cu(II), which joins terminal square pyramidal Cu(II), was coordinated only by the phenolic oxygens of the ligand while the central Ni(II) was coordinated by two phenolic oxygens of the organic ligand and two water molecules. These complexes were investigated by XPS and it was found that the terminal and central Cu2+ ions were different in Cu(II)–Cu(II)–Cu(II) complex. Also, the thermal degradation of the CuLH complex unit was observed to exothermic in contrast to the expectations. 相似文献
17.
Complexes of Co(II), Ni(II), Cu(II), and Zn(II) with N, N′-(aldose) 2–thiocarbohydrazide (LH 2) were synthesized, isolated as solid products and characterized by analytical means as well as by spectral techniques, FTIR, 1H NMR, EPR, UV spectroscopy, and CD. All the metal ions formed M[LH]X complexes. Molar conductance values in DMF indicate non-electrolytic complexes. In DMSO with tetramethylammonium chloride supporting electrolyte, the copper complex displays irreversible cyclic voltammetric responses with E p near ?0.621 and 0.461 V versus Ag/AgCl at scan rate of 0.1 V s ?1. Probable structures for the complexes are proposed. 相似文献
18.
Four new ternary complexes of Cu II with l-methionine and the nucleotides 5AMP (adenosine 5-phosphate), 5GMP (guanosine 5-phosphate) and 5IMP (inosine 5-phosphate), and with l-tryptophan and 5AMP, were synthesized and characterized by elemental analysis and i.r. spectroscopy. One ternary complex of N II with l-cysteine and 5IMP was also prepared and characterized. The study of the three ternary compounds of Cu II, of general formulae Cu-5NMP-l-methionine, indicates coordination of the phosphate group and of N(7) of the purinic ring. l-Methionine is bound by the carboxylic and amino groups. The ternary complex obtained from a mixture of Cu-5AMP and l-tryptophan is a dimer in which the nucleotide bridges the two copper atoms. In the complex of Ni-5IMP and l-cysteine, the nucleotide seems to bind the metal through the N(7) of the heterocyclic ring, and the l-cysteine is coordinated as a bidentate chelate by the carboxyl and thiol groups. E.s.r. spectra of the copper complexes are in good agreement with the low symmetry structure proposed. The one-electron reduction potentials E c(Fc +/Fc) (V) of Cu II to Cu I were established for the four copper complexes from cyclic voltammetry studies. The one-electron oxidation potential E a(Fc +/Fc +) (V) of Ni II to Ni III was also measured for the nickel complex. 相似文献
19.
Introduction The complexes of amino acid Schiff base have re-ceived considerable attention because of the interests in the biogical field.1-4 Taurine is a special amino acid in human beings. Recently, the complexes of taurine con-densation salicylaldelyde Schiff base have been re-ported,3-7 but the complexes of taurine condensation derived salicylaldelyde Schiff base have not been re-ported yet. In order to examine its anticancer and antibiosis ac-tivity of the complexes of taurine condensa… 相似文献
20.
A series of metal ion complexes was prepared in solid state from Cu(II), Hg(II) and UO 2(II) ions with 3-oxo-3-(2-(2-oxoindolin-3-ylidene)hydrazineyl)-N-phenylpropanamide (H 3L) ligand through solvent free synthesis methodology. The chemical formulae of the new compounds were estimated according to variable spectral and analytical investigations. The ligand exhibited a neutral or mononegative tetradentate mode of coordination towards the central ions inside the octahedral arrangement that proposed for the three complexes. The DFT/B3LYP method was applied under different basis sets (6-31G*or SDD) to optimize the structures of new compounds except the UO 2(II) complex. The computational data were investigated to verify the binding mode that suggested spectrally. Moreover, studies in solution regarding Cu(II) ion via cyclic voltammetry were performed in absence or presence of H 3L, to realize the significant effect of complex formation on the electrochemical manners of copper. The shifts in the potential peaks accompanied by the changes in the values of parameters correspond to kinetic and thermodynamic. Also, the solvation and kinetic characteristics for the cathodic and anodic potential of Cu(II) ion in absence or presence of H 3L at different scan rates, were estimated. Finally, the ligand and copper ion exhibited high affinity towards complexation in solution. Furthermore, the activity of the new compounds towards inhibiting microbes was studied against Staphylococcus aureus (G+) and Escherichia coli ( G-) bacteria as well as Candida albicans (fungus) by determining the inhibition zone diameter. Also, both the antioxidant and cytotoxic activity of the isolated compounds were evaluated. Commonly, a remarkable antimicrobial and anticancer activity was appeared with UO 2(II) complex and the ligand. While, the antioxidant activity of all compounds appeared lower. 相似文献
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