Equilibrium, 1H and 13C NMR spectroscopy, and X-ray diffraction studies on the complexes Bi(DOTA)- and Bi(DO3A-Bu)

Éva Csajbók, Zsolt Baranyai, István Bányai, Ernó Brucher, Róbert Király, Anke Muller-Fahrnow, Johannes Platzek, Bernd Raduchel, Martina Schäfer

Research output: Article

36 Citations (Scopus)


Several Bi(III) complexes are used in medicine as drugs. Bi(DO3A-Bu) has recently been proposed as a nonionic contrast agent in X-ray imaging (H3DO3A-Bu = 10-[2,3-dihydroxy-(1-hydroxymethyl)propyl]-1,4,7, 10-tetraazacyclododecane-1,4,7,-triacetic acid). The solution equilibria and NMR structure and dynamics of Bi(DO3A-Bu) and of the similar Bi(DOTA)- have been investigated (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid). The stability constants were determined with the study of the competition equilibria between Br- ions and the ligands DOTA or DO3A-Bu for the Bi(III) by spectrophotometry, The stability constants, obtained for Bi(DOTA)-and Bi(DO3A-Bu), are very high, log K= 30.3 and 26.8, respectively. Potentiometric titrations indicated the dissociation of one of the protons among the three alcoholic OH groups in Bi(DO3A-Bu). The dissociation constant is log K = 7.53 (0.09) indicating that at physiological pH about 50% of the species possess -1 charge. It was shown by 1H and 13C NMR spectroscopy that the OH group attached to the middle carbon atom of the "butriol" side chain is coordinated to the Bi(III) and starts to deprotonate at pH > 5.5. The crystal structure of NaBi(DOTA)·H2O shows an octacoordinated arrangement of the donor atoms around the Bi(III), with no water in the inner sphere. The crystals belong to the centrosymmetric space group C2/c. The temperature dependent 1H and 13C NMR spectra indicate that both Bi(DOTA)- and Bi(DO3A-Bu)- complexes are fluxional. For Bi(DOTA), the Δ(δδδδ) ⇄ Λ(λλλλ) fluxionality was identified, and on the basis of the activation parameters, a synchronous motion was suggested for the fluxional motion resulting in the change of ring conformation and of the helicity of the complex. The transition state is supposed to be more symmetrical than the initial state. The deprotonated Bi(DO3A-Bu) has a highly asymmetric NMR structure in solution, and its fluxional motion is slower than that of Bi(DOTA)-.

Original languageEnglish
Pages (from-to)2342-2349
Number of pages8
JournalInorganic Chemistry
Issue number7
Publication statusPublished - ápr. 7 2003

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Equilibrium, <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy, and X-ray diffraction studies on the complexes Bi(DOTA)- and Bi(DO3A-Bu)'. Together they form a unique fingerprint.

  • Cite this