Dataset Information

Correlation of relaxivity with coordination number in six-, seven-, and eight-coordinate Mn(II) complexes of pendant-arm cyclen derivatives.

ABSTRACT: The syntheses and characterization of several complexes of Mn(II) with cyclen derivatives having variable numbers of pendant N-acetic acid or N-acetamide arms are reported. X-ray crystallographic results are presented for Mn(DOTAM)Cl(2) x 2 H(2)O (monoclinic C2/c, a = 18.5798(15), b = 13.6006(11), c = 10.5800(8) A, beta = 110.490(1) degrees, Z = 4), [Mn(DO3AM)][MnCl(4)] x EtOH (monoclinic P2(1)/n, a = 8.366(8), b = 19.483(2), c = 16.3627(16) A, beta = 99.254(2) degrees, Z = 4), and Mn(H(2)DOTA) (monoclinic C2/c, a = 16.374(3), b = 6.6559(13), c = 16.750(3) A, beta = 98.381(3) degrees, Z = 4), which exhibit 8-, 7-, and 6-coordinate Mn(II), respectively. (1)H relaxivity data in water at 20 MHz and 37 degrees C is presented and interpreted in terms of a mechanism involving transient binding of water in an associative intermediate. Relaxivity studies in mixed water/methanol solvents are consistent with this interpretation.

SUBMITTER: Wang S

PROVIDER: S-EPMC2682917 | biostudies-literature | 2009 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Correlation of relaxivity with coordination number in six-, seven-, and eight-coordinate Mn(II) complexes of pendant-arm cyclen derivatives.

Wang Sen S Westmoreland T David TD

Inorganic chemistry 20090101 2

The syntheses and characterization of several complexes of Mn(II) with cyclen derivatives having variable numbers of pendant N-acetic acid or N-acetamide arms are reported. X-ray crystallographic results are presented for Mn(DOTAM)Cl(2) x 2 H(2)O (monoclinic C2/c, a = 18.5798(15), b = 13.6006(11), c = 10.5800(8) A, beta = 110.490(1) degrees, Z = 4), [Mn(DO3AM)][MnCl(4)] x EtOH (monoclinic P2(1)/n, a = 8.366(8), b = 19.483(2), c = 16.3627(16) A, beta = 99.254(2) degrees, Z = 4), and Mn(H(2)DOTA) ...[more]

PMID: 19072697

Similar Datasets

Project description:The Cu2+ complexes formed by a series of cyclen derivatives bearing sulfur pendant arms, 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-10-acetamido-1,4,7,10-tetraazacyclododecane (DO3SAm), and 1,7-bis[2-(methylsulfanyl)ethyl]-4,10-diacetic acid-1,4,7,10-tetraazacyclododecane (DO2A2S), were studied in aqueous solution at 25 °C from thermodynamic and structural points of view to evaluate their potential as chelators for copper radioisotopes. UV-vis spectrophotometric out-of-cell titrations under strongly acidic conditions, direct in-cell UV-vis titrations, potentiometric measurements at pH >4, and spectrophotometric Ag+-Cu2+ competition experiments were performed to evaluate the stoichiometry and stability constants of the Cu2+ complexes. A highly stable 1:1 metal-to-ligand complex (CuL) was found in solution at all pH values for all chelators, and for DO2A2S, protonated species were also detected under acidic conditions. The structures of the Cu2+ complexes in aqueous solution were investigated by UV-vis and electron paramagnetic resonance (EPR), and the results were supported by relativistic density functional theory (DFT) calculations. Isomers were detected that differed from their coordination modes. Crystals of [Cu(DO4S)(NO3)]·NO3 and [Cu(DO2A2S)] suitable for X-ray diffraction were obtained. Cyclic voltammetry (CV) experiments highlighted the remarkable stability of the copper complexes with reference to dissociation upon reduction from Cu2+ to Cu+ on the CV time scale. The Cu+ complexes were generated in situ by electrolysis and examined by NMR spectroscopy. DFT calculations gave further structural insights. These results demonstrate that the investigated sulfur-containing chelators are promising candidates for application in copper-based radiopharmaceuticals. In this connection, the high stability of both Cu2+ and Cu+ complexes can represent a key parameter for avoiding in vivo demetalation after bioinduced reduction to Cu+, often observed for other well-known chelators that can stabilize only Cu2+.

Dataset Information

Correlation of relaxivity with coordination number in six-, seven-, and eight-coordinate Mn(II) complexes of pendant-arm cyclen derivatives.

Publications

Correlation of relaxivity with coordination number in six-, seven-, and eight-coordinate Mn(II) complexes of pendant-arm cyclen derivatives.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets