Synthesis and characterization of novel 99gTc(V) and Re(V) complexes with water-soluble tetraaza diamido dipyridino ligands: Single-crystal X-ray structural investigations of mono- and dinuclear complexes

Laszlo Kurti, Dioni Papagiannopoulou, Minas Papadopoulos, Ioannis Pirmettis, Catherine P. Raptopoulou, Aris Terzis, Efstratios Chiotellis, Michael Harmata, Robert R. Kuntz, Raghoottama S. Pandurangi

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15 Scopus citations

Abstract

Rhenium and technetium are known for their useful applications in nuclear medicine with similar properties. In this study, new diamido dipyridino (N4) water-soluble ligands (2-C5H4NCH2NHCO)2CH2, 1 (L1H2), (2-C5H4NNHNHCO)2CH2, 2, and [2-C5H4N+(O)-CH2 NHCO]2CH2, 3, were synthesized. Reaction of L1H2 with ReOCl3(PPh3)2 resulted in the novel six-coordinated rhenium(V) complex, trans-ReO(L1) (OEt), 4. The complex was characterized by spectroscopic methods, and its X-ray crystallographic analysis revealed that rhenium is coordinated to four nitrogen atoms of the ligand and to two oxygen atoms from the deprotonated ethanol and the oxo group respectively in a distorted octahedral geometry. In solution, complex 4 was transformed to a new complex 5, which was proved to be the dinuclear complex μ-oxo [ReO(L1)]2O. Reaction of 1 with [n-Bu4N][ReOCl4] resulted in the neutral complex 6, trans-[ReO(L1)]Cl. Similarly, when ligand 1 was reacted with [n-Bu4N][99gTcOCl4], neutral trans-(99TcO(L1)]Cl complex 7 was formed, which upon dissolution transformed into a cationic complex 8, trans-[99TcO(L1)(OH2)]+ Cl-. The single-crystal X-ray structure of 8 reveals that the coordination sphere about technetium is a distorted octahedron with four nitrogen atoms in the equitorial plane, while doubly bonded oxygen and coordinated water occupy the apical positions. Further dissolution of 8 resulted in the formation of dinuclear μ-oxo [TcO(L1)2O, 9, This study shows that Tc and Re have similar metal core structures in solution for diamido dipyridino systems, besides similarity in geometrical structure, proved by the X-ray structures on the same ligands.

Original languageEnglish (US)
Pages (from-to)2960-2967
Number of pages8
JournalInorganic Chemistry
Volume42
Issue number9
DOIs
StatePublished - May 5 2003

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Kurti, L., Papagiannopoulou, D., Papadopoulos, M., Pirmettis, I., Raptopoulou, C. P., Terzis, A., Chiotellis, E., Harmata, M., Kuntz, R. R., & Pandurangi, R. S. (2003). Synthesis and characterization of novel 99gTc(V) and Re(V) complexes with water-soluble tetraaza diamido dipyridino ligands: Single-crystal X-ray structural investigations of mono- and dinuclear complexes. Inorganic Chemistry, 42(9), 2960-2967. https://doi.org/10.1021/ic020434q