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CdII Complex (cdii + complex)
Selected AbstractsMacrocyclic Receptor Showing Improved PbII/ZnII and PbII/CaII SelectivitiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2010Raquel Ferreirós-Martínez Abstract Herein we report on the macrocyclic receptor N,N,-bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-15-crown-5 (H2bp15c5) and its coordination properties towards ZnII, CdII, PbII, and CaII. The stability constants of these complexes determined by pH-potentiometric titration at 25 °C in 0.1 M KNO3 vary in the following order: PbII > CdII >> ZnII > CaII. As a result, bp15c5 presents very important PbII/ZnII and PbII/CaII selectivities. These results are in contrast to those reported for the related receptor derived from 1,7-diaza-12-crown-4, which provides very similar complex stabilities for ZnII and PbII. The X-ray crystal structure of [Cd(Hbp15c5)]+ shows heptadentate binding of the ligand to the metal ion, with two oxygen atoms of the macrocyclic unit remaining uncoordinated. The 1H NMR spectra of the complexes formed with PbII, ZnII, and CaII (D2O) show very broad peaks in the region 2,5 ppm, indicating an important degree of flexibility of the crownmoiety in these complexes. On the contrary, the 1H and 13C NMR spectra recorded for the CdII complex are well resolved and could be fully assigned. A detailed conformational investigation using theoretical calculations performed at the DFT (B3LYP) level predict a minimum energy conformation for [Cd(bp15c5)] that is very similar to that observed in the solid state. Analogous calculations performed on the [M(bp15c5)] (M = Zn or Pb) systems predict hexadentate binding of the ligand to these metal ions. In the case of the PbII complex our calculations indicate that the 6s lone pair is stereochemically active, which results in a hemidirected coordination geometry around the metal ion. The minimum energy conformations calculated for the ZnII, CdII, and PbII complexes are compatible with the experimental NMR spectra obtained in D2O solution. [source] One-Dimensional Oxalato-Bridged Metal(II) Complexes with 4 - Amino-1,2,4-triazole as Apical LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2005Urko García-Couceiro Abstract The synthesis, chemical characterization, thermal behavior and magnetic properties of six new one-dimensional oxalato-bridged metal(II) complexes of formula [M(,-ox)(4atr)2]n [MII = Cu (1), Ni (2), Co (3), Zn (4), Fe(5)] and [Cd(,-ox)(4atr)2(H2O)]n (6) (ox = oxalato dianion, 4atr = 4-amino-1,2,4-triazole) are reported. The crystal structures of 1 and 6 have been solved by single-crystal X-ray diffraction, whereas the remaining compounds have been studied by means of X-ray powder diffraction methods. Compounds 1,5 are isomorphous and crystallize in the triclinic space group P1¯ with unit cell parameters for 1 of a = 5.538(1) Å, b = 7.663(1) Å, c = 7.711(2) Å, , = 62.21(1)°, , = 73.91(1)°, , = 86.11(1)°, and Z = 1. The crystal structures are comprised of one-dimensional linear chains in which the trans -[M(4atr)2]2+ units are sequentially bridged by bis(bidentate) oxalato ligands, resulting in an octahedral O4N2 donor set. Cryomagnetic susceptibility measurements show the occurrence of antiferromagnetic intrachain interactions for 2, 3, and 5, whereas compound 1 exhibits a weak ferromagnetic coupling in agreement with the out-of-plane exchange pathway involved. The magnetic behavior of 1 and 2 is analyzed and discussed in the light of the available magneto-structural data for analogous systems. CdII complex crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 16.128(2) Å, b = 6.757(1) Å, c = 11.580(2) Å, , = 104.46(1)°, and Z = 4. Its crystal structure contains one-dimensional chains in which metal centers are heptacoodinated to four oxygen atoms from two symmetry-related bis(bidentate) oxalato bridges, two endocyclic nitrogen atoms of trans -coordinated triazole ligands and one water molecule, to give a CdO4OwN2 pentagonal-bipyramidal geometry. Thermoanalytical and variable-temperature X-ray powder diffraction analyzes show that compound 6 undergoes a reversible dehydration,hydration process in which the anhydrous residue crystallizes with a different crystal lattice retaining the dimensionality of the oxalato,metal framework. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Di-,-acesulfamato-,3N,O:O;,3O:N,O -bis[(acesulfamato-,2N,O)bis(3-methylpyridine)cadmium(II)]ACTA CRYSTALLOGRAPHICA SECTION C, Issue 12 2009Zarife Sibel In the structure of the title compound, [Cd2(C4H4NO4S)2(C6H7N)2], the dinuclear CdII complex is located on a twofold axis with two Cd2+ ions bridged by two oxide O atoms. Each Cd2+ ion is additionally coordinated in an equatorial plane by two N and three O atoms of the acesulfamate ligands and axially by two N atoms of the 3-methylpyridine ligands, resulting in a distorted pentagonal bipyramidal coordination. We present here an example of a supramolecular assembly based on hydrogen bonds in a mixed-ligand metal complex; intermolecular C,H...O hydrogen bonds give rise to R44(40) rings, which lead to one-dimensional chains. [source] Metal Ion Complementarity: Effect of Ring-Size Variation on the Conformation and Stability of Lead(II) and Cadmium(II) Complexes with Pendant-Armed CrownsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2007Martín Regueiro-Figueroa Abstract The binding tendencies of the pendant-armed crown ethers L1,L3 [L1 = N,N, -bis(benzimidazol-2-ylmethyl)-1,7-diaza-12-crown-4, L2 = N,N, -bis(benzimidazol-2-ylmethyl)-1,10-diaza-15-crown-5) and L3 = N,N, -bis(benzimidazol-2-ylmethyl)-4,13-diaza-18-crown-6] towards PbII and CdII have been investigated. The X-ray crystal structure of [Cd(L3)](ClO4)2·EtOH shows that, in the solid state, the CdII ion is eight-coordinate and fits quite well into the crown hole, favouring an anti arrangement of the organic receptor. NMR measurements recorded in acetonitrile solution indicate that increasing the crown size induces a conformational change in the series of CdII complexes. The conformation goes from a syn arrangement for L1 to an anti arrangement for L3, passing through a syn [lrarr2] anti equilibrium in the complex derived from L2. On the contrary, no conformational change was observed for the corresponding PbII complexes, which have a syn conformation in all cases. These results have been confirmed by means of density functional theory (DFT) calculations performed by using the B3LYP model. The binding constants obtained from UV/Vis titration experiments in DMSO solution demonstrate that a decrease in the crown size provokes a 102 -fold enhancement of the stability for this series of CdII complexes, whereas for PbII a gradual decrease of the binding constants is observed. Receptor L1 shows a certain degree of selectivity for CdII over PbII, with a selectivity factor > 102. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Non-Covalent Aggregation of Discrete Metallo-Supramolecular Helicates into Higher Assemblies by Aromatic Pathways: Structural and Chemical Studies of New Aniline-Based Neutral Metal(II) DihelicatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2005Miguel Vázquez Abstract Neutral manganese(II), iron(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) complexes with an N -tosyl-substituted N4 -donor Schiff base containing a 4,4'-methylenedianiline residue as spacer [H2La: N,N' -bis(2-tosylaminobenzylidene)-4,4'-methylenedianiline], and the zinc(II) complex with an analogous ligand [H2Lb: N,N' -bis(2-tosylaminobenzylidene)-4,4'-oxodianiline] have been prepared by an electrochemical procedure. FAB and ESI mass spectra of the complexes show peaks due to species corresponding to a general formula [M2(La,b)2 + H]+, thereby suggesting their dinuclear nature. A detailed study of the crystal packing in the unit cell of the zinc(II) complex with H2La shows that the helicates aggregate to form discrete prismatic moieties containing three molecules held together by ,,, and ,,, interactions. Moreover, the ZnII neutral dihelicate with H2Lb forms a 3D network in the solid state due to intermolecular ,-stacking interactions. 1H NMR studies of the diamagnetic compounds reported herein have been performed. Finally, the ligand H2La and its ZnII and CdII complexes have been studied by spectrophotometric and spectrofluorimetric techniques in order to get a better understanding of the formation mechanisms of the complexes and of the nature of their fluorescence emission. Emission studies show that the ZnII and CdII dihelicates with H2La display a green fluorescence in acetonitrile solution (, = 473 nm, , = 0.03 and , = 476 nm, , = 0.01, respectively). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] | ||||||||||