The cobalt(II) complex
salts [Co(bpy)(az)2](PF6)2 and [Co(az)4](PF6), each bearing
the unusual cis-N,N′-diphenylazodioxide ligand, were both screened as possible
anticancer agents against SK-HEP-1 liver cancer cells. Both compounds
were found to induce substantial apoptosis as an increasing function
of concentration and time. Measurement of apoptosis-related proteins
indicated that both the extrinsic and intrinsic pathways of apoptosis
were activated. The apoptotic activity induced by these salts is not
displayed either by simple cobalt(II) salts or complexes or by the
free nitrosobenzene ligand. Additionally, these compounds did not
induce apoptosis, as assessed by poly(adenosine diphosphate-ribose)
polymerase cleavage, in several other cell lines.
Removal
of chloride from CoCl
2
with TlPF
6
in acetonitrile,
followed by addition of excess nitrosobenzene,
yielded the eight-coordinate cobalt(II) complex salt [Co{Ph(O)NN(O)Ph}
4
](PF
6
)
2
, shown by single-crystal X-ray
analysis to have a distorted tetragonal geometry. The analogous treatment
of the bipyridyl complex Co(bpy)Cl
2
yielded the mixed-ligand
cobalt(II) complex salt [Co(bpy){Ph(O)NN(O)Ph}
2
](PF
6
)
2
, whose single-crystal X-ray structure displays
a trigonal prismatic geometry, similar to that of the iron(II) cation
in the previously known complex salt [Fe{Ph(O)NN(O)Ph}
3
](FeCl
4
)
2
. The use of TlPF
6
to generate
solvated metal complex cations from chloride salts or chlorido complexes,
followed by the addition of nitrosobenzene, is shown to be a useful
synthetic strategy for the preparation of azodioxide complex cations
with the noncoordinating, diamagnetic PF
6
–
counteranion. Coordination number appears to be more important than
d
electron count in determining the geometry and metal–ligand
bond distances of diphenylazodioxide complexes.
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