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Metal-ion Complexes (metal-ion + complex)

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Chemistry	50%

Selected Abstracts

Structure, Characterization, and Metal-Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant Arms

HELVETICA CHIMICA ACTA, Issue 10 2004
Xiuling Cui
The new tetraazamacrocycle 2 (=2,2,-[[7-Methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene-3,11-diyl]bis(methylene)]bis(4-bromophenol)) was synthesized and used as a ligand for different metal-ion complexes. The X-ray crystal structures of the complexes of the general formula [M(H- 2)]+NO,MeOH (M=Ni2+, Zn2+), in which only one of the two pendant phenolic OH groups of 2 is deprotonated, were determined. In both complexes, the coordination environment is of the [5+1] type, the four N-atoms of the macrocyclic framework defining a square-planar arrangement around the metal center, with similar NiN and ZnN distances of 1.961(9) to 2.157(9),Å and 2.021(9) to 2.284(8),Å, respectively. In contrast, the MO distances are markedly different, 2.060(6) and 2.449(8),Å in the NiII complex, and 2.027(7) and 2.941(9),Å in the ZnII complex. The UV/VIS spectra of the NiII and CuII complexes with ligand 2, and the EPR spectra of the CuII system, suggest the same type of structure for the complexes in solution as in the solid state. Theoretical studies by means of density functional theory (DFT) confirmed the experimental structures of the NiII and ZnII complexes, and led to a proposal of a similar structure for the corresponding CuII complex. The calculated EPR parameters for the latter and comparison with related data support this interpretation. The singly occupied molecular orbital (SOMO) in these systems is mainly made of a d orbital of Cu, with a strong antibonding (,*) contribution of the axially bound phenolate residue. [source]

Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activities

JOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008
K. C. Gupta
Abstract Polymer-supported transition-metal-ion complexes of the N,N,-bis(o -hydroxy acetophenone) propylenediamine (HPPn) Schiff base were prepared by the complexation of iron(III), cobalt(II), and nickel(II) ions on a polymer-anchored N,N,-bis(5-amino- o -hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III), cobalt(II), and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44, 82.92, and 89.58 wt%, respectively, whereas the unsupported HPPn Schiff base showed 82.29, 81.18, and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry, whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape, as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions, as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500°C, but its iron(III), cobalt(II), and nickel(II) ion complexes showed weight losses of 27.0, 35.0, and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene, but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions, but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol, respectively, but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III), cobalt(II), and nickel(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008 [source]

Lanthanide(III) Complexes of 4,10-Bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans -H6do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

CHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2010
M. Paula
Abstract Complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans -H6do2a2p, H6L) with transition metal and lanthanide(III) ions were investigated. The stability constant values of the divalent and trivalent metal-ion complexes are between the corresponding values of H4dota and H8dotp complexes, as a consequence of the ligand basicity. The solid-state structures of the ligand and of nine lanthanide(III) complexes were determined by X-ray diffraction. All the complexes are present as twisted-square-antiprismatic isomers and their structures can be divided into two series. The first one involves nona-coordinated complexes of the large lanthanide(III) ions (Ce, Nd, Sm) with a coordinated water molecule. In the series of Sm, Eu, Tb, Dy, Er, Yb, the complexes are octa-coordinated only by the ligand donor atoms and their coordination cages are more irregular. The formation kinetics and the acid-assisted dissociation of several LnIII,H6L complexes were investigated at different temperatures and compared with analogous data for complexes of other dota-like ligands. The [Ce(L)(H2O)]3, complex is the most kinetically inert among complexes of the investigated lanthanide(III) ions (Ce, Eu, Gd, Yb). Among mixed phosphonate,acetate dota analogues, kinetic inertness of the cerium(III) complexes is increased with a higher number of phosphonate arms in the ligand, whereas the opposite is true for europium(III) complexes. According to the 1H,NMR spectroscopic pseudo-contact shifts for the Ce,Eu and Tb,Yb series, the solution structures of the complexes reflect the structures of the [Ce(HL)(H2O)]2, and [Yb(HL)]2, anions, respectively, found in the solid state. However, these solution NMR spectroscopic studies showed that there is no unambiguous relation between 31P/1H lanthanide-induced shift (LIS) values and coordination of water in the complexes; the values rather express a relative position of the central ions between the N4 and O4 planes. [source]