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By Werner Krause (Editor)

ISBN-10: 3540422471

ISBN-13: 9783540422471

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19, respectively [131], whereas the [Eu(DOTTA)]3+ has a m/M ratio of 2 with the predominant isomer having the twisted SAP geometry. These results indicate that a twisted SAP structure is preferred with increasing steric demand at the metal center, as found before for tetracarboxylate [75, 78, 79] and tetraphosphinate [109, 110] derivatives. The ratio of the two isomers for [Ln(DOTAM)]3+ complexes depends on temperature, solvent and the nature of the Ln3+ ion. Luminescence lifetime measurements of the DOTAM, DTMA and DOTTA Eu3+ complexes revealed the existence of one bound water molecule [127, 136].

A low barrier between the 8-coordinate ground state and 9-coordinate transition state in the associative exchange mechanism can explain the rapid exchange rates. The small difference in stability between 8- and 9-coordinate complexes of this type is supported by the occurrence of both coordination structures in a crystal of La[TREN-Me-3,2-HOPO] [58]. 1 DOTA and Derivatives Ln3+ induced water 17O shifts of [Ln(DOTA)]– solutions show that the hydration number of the complexes is one across the lanthanide series [59].

It can be concluded that this compound occurs as at least two pairs of interconverting isomers [28]. In principle, the chirality in the benzyloxymethyl chain can give rise to doubling of the number of isomers, however, they are probably not observable in the NMR spectra of the diamagnetic La3+ and Lu3+ complexes due to small chemical shift differences between them. In the solid state structure of Na2[Gd(BOPTA)], two enantiomeric forms (trans, see Fig. 1) occur in each unit cell [28]. Two diastereomeric Gd(S-EOB-DTPA) complexes have been isolated by preparative HPLC [29].

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Contrast Agents I: Magnetic Resonance Imaging (Topics in Current Chemistry, 221) by Werner Krause (Editor)

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