Alkaline Earth Metal and Lanthanide(III) Complexes of Ligands Based upon 1,4,7,10-Tetraazacyclododecane-1,7-bis(acetic acid)

Jurriaan Huskens; Diego A. Torres; Zoltan Kovacs; João P. André; Carlos F. G. C. Geraldes; A. Dean Sherry

doi:10.1021/ic961131x

Alkaline Earth Metal and Lanthanide(III) Complexes of Ligands Based upon 1,4,7,10-Tetraazacyclododecane-1,7-bis(acetic acid)

Inorg Chem. 1997 Mar 26;36(7):1495-1503. doi: 10.1021/ic961131x.

Authors

Jurriaan Huskens¹, Diego A. Torres, Zoltan Kovacs, João P. André, Carlos F. G. C. Geraldes, A. Dean Sherry

Affiliation

¹ Department of Chemistry, University of Texas at Dallas, P.O. Box 830688, Richardson, Texas 75083-0688, Department of Chemistry, School of Sciences, University of Minho, 4714 Braga, Portugal, Department of Biochemistry and Center of Neurosciences, Faculty of Science and Technology, University of Coimbra, Apartado 3126, 3000 Coimbra, Portugal, and Department of Radiology, Rogers Magnetic Resonance Center, University of Texas Southwestern Medical Center, Dallas, Texas 75235-9085.

PMID: 11669731
DOI: 10.1021/ic961131x

Abstract

The macrocyclic ligand DO2A (1,4,7,10-tetraazacyclododecane-1,7-bis(acetic acid)) was prepared and used as a building block for four new macrocyclic ligands having mixed side-chain chelating groups. These ligands and their complexes with Mg(II), Ca(II), and Ln(III) were studied extensively by potentiometry, high-resolution NMR, and water proton relaxivity measurements. The protonation constants of all compounds compared well with those of other cyclen-based macrocyclic ligands. All Ca(II) complexes were found to be more stable than the corresponding Mg(II) complexes. Trends for the stabilities of the Ln(III) complexes are discussed and compared with literature data, incorporating the effects of water coordination numbers, Ln(III) contraction, and the nature of the side chains and the steric hindrance between them. (1)H NMR titrations of DO2A revealed that the first and second protonations take place preferentially at the secondary ring nitrogens, while the third and fourth involved protonation of the acetates. (17)O NMR shifts showed that the DyDO2A(+) complex had two inner-sphere water molecules. Water proton spin-lattice relaxation rates for the GdDO2A(+) complex were also consistent with water exchange between bulk water and two inner-sphere Gd(III) coordination positions. Upon formation of the diamagnetic complexes of DO2A (Ca(II), Mg(II), La(III), and Lu(III)), all of the macrocyclic ring protons became nonequivalent due to slow conformational rearrangements, while the signals for the acetate CH(2) protons remained a singlet.