Insight into the structure and stability of Tc and Re DMSA complexes: A computational study

[Display omitted] •Structural and stability DFT calculation of Tc and Re DMSA complexes are reported.•MAS-3 is proposed as new more stable structure to 99mTc(III)-DMSA radiopharmaceutical.•AIM confirmed that strongest metal-ligand interactions are obtained for MAS-3 complex.•Tc(V)-DMSA isomers are more stable than Tc(III)-DMSA complexes.•The strength of MO and MS bonds goes from pure dative bonds to weak interactions. Meso-2,3-dimercaptosuccinic acid (DMSA) is used in nuclear medicine as ligand for preparation of diagnostic and therapy radiopharmaceuticals. DMSA has been the subject of numerous investigations during the past three decades and new and significant information of the chemistry and pharmacology of DMSA complexes have emerged. In comparison to other ligands, the structure of some DMSA complexes is unclear up today. The structures and applications of DMSA complexes are strictly dependent on the chemical conditions of their preparation, especially pH and components ratio. A computational study of M-DMSA (M=Tc, Re) complexes has been performed using density functional theory. Different isomers for M(V) and M(III) complexes were studied. The pH influence over ligand structures was taken into account and the solvent effect was evaluated using an implicit solvation model. The fully optimized complex syn-endo Re(V)-DMSA shows a geometry similar to the X-ray data and was used to validate the methodology. Moreover, new alternative structures for the renal agent 99mTc(III)-DMSA were proposed and computationally studied. For two complex structures, a larger stability respect to that proposed in the literature was obtained. Furthermore, Tc(V)-DMSA complexes are more stable than Tc(III)-DMSA proposed structures. In general, Re complexes are more stable than the corresponding Tc ones.