Dimeric W3SO3 Cluster Complexes: Synthesis, Characterization, and Potential Applications as X-ray Contrast Agents

Abstract
Our continued research on the use of heavy metal cluster complexes as a new class of X-ray contrast agents in medical diagnostic imaging is described. A series of 2:3 cluster−ligand complexes, [(WIV3SO3)2L3]4- (L = linear polyaminopolycarboxylate ligands), were isolated from the reaction of aqua ion [WIV3SO3(H2O)9]4- (prepared in large quantities through an improved literature process) with respective ligands in refluxing DMF. The salts of [(WIV3SO3)2L3]4- complex anions were fully characterized using routine techniques such as elemental analysis, MS, HPLC, UV−vis, IR, and NMR. The solid structures of two complex anions, [(WIV3SO3)2(PDTA)3]4- and [(WIV3SO3)2(HO−PDTA)3]4-, were determined by X-ray crystallography. They are the first examples wherein two WIV3SO3 clusters are complexed and linked by three ligands that contain two terminal iminodiacetate (bis-IDA) groups. Complexation of the unstable aqua ion [WIV3SO3(H2O)9]4- with ligands has imparted desired biological compatibility to the tungsten metal cluster. These complexes are stable and highly soluble in H2O. The potential utility of such tungsten cluster complexes as X-ray contrast agents was evaluated in both in vitro and in vivo animal studies. In addition, the syntheses of several new linear polyaminopolycarboxylate ligands used in this study are reported.

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