Technetium and rhenium oxo-complexes of new tetradentate ligands with N2S2 and NS3 donor sets
Abstract
A series of new tetradentate, nitrogen–sulfur donor proligands
with amido or amino donor groups have been synthesized and their rhenium
and technetium oxo-complexes prepared. The substitution pattern and
length of the ligand backbone can be varied without affecting the
co-ordination chemistry. The NS
3
H
3
amido-proligands reacted rapidly with the technetium(V)
precursor [TcOCl
4
]
-
at reflux in methanol to
give the technetium(IV) species
[TcO(NS
3
)]
-
in very high radiochemical
purity (ca. 100%), but these complexes decompose over a period
of hours or days. They also reacted with the rhenium(V)
precursors [ReO
2
(py)
4
]Cl
(py = pyridine) or
[ReOCl
3
(PPh
3
)
2
] at reflux in methanol,
but only in the presence of a base. Stable neutral rhenium(V)
complexes of the type [ReO(NS
3
)] were formed, and the crystal
structures of two determined. A reduced amino version of the
NS
3
H
3
proligand gave an analogous
[ReO(NS
3
)] complex, and its crystal structure was
determined.
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