The synthesis, at tracer level, of two Tc-99m complexes having the same chemical composition
and structure, but differing by one electron in the total electron counting, is reported. These compounds have
been prepared by reacting [99mTcO4]2 with the piperidinium salt of the ligand ferrocenedithiocarboxylate
[Fe(II)(C5H4CS2)(C5H5)]25FcCSgroups,andtriphenylphosphineorSnCl2asreducingagents.Theformationoftheneutralcomplex[99mTc(N)(FcCS)2](compoundA)andofthemonocationic,mixed−valencecomplex[99mTc(N)(FcCS)(FcCS∗)]1(compoundB)FcCS* 5 [Fe(III)(C5H4CS2)(C5H5)]% was obtained in high yield. Both complexes
comprise a terminal Tc [ N multiple bond and two FcCS ligands coordinated to the metal center through the
two sulfur atoms of the -CS2 group, but they differ in the oxidation state of one of the two iron atoms of the
coordinated FcCS ligands. In complex A, the two Fe atoms are both in the 12 oxidation state, while in B, one
Fe atom is in the 12 and the other is in the 13 oxidation state. Thus, B is a mixed-valence Fe(II)-Fe(III)
complex. B is easily converted into A by one-electron exchange with various reductants such as triphenylphosphine
and excess SnCl2. Biodistribution studies in rats showed that complexes A and B are mostly
retained in lungs and liver without any significant uptake in organs such as heart and brain
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