Influence of Tetraazamacrocyclic
Ligands on the Nitric
Oxide Reactivity of their Cobalt(II) Complexes
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Abstract
The reactions of cobalt(II) complexes of tetraazamacrocyclic
tropocoronand
(TC) ligands with nitric oxide (NO) were investigated. When [Co(TC-5,5)]
was allowed to react with NO(g), the {CoNO}<sup>8</sup> mononitrosyl
[Co(NO)(TC-5,5)] was isolated and structurally characterized. In contrast,
a {Co(NO)<sub>2</sub>}<sup>10</sup> species formed when [Co(TC-6,6)]
was exposed to NO(g), and the nitrito [Co(NO<sub>2</sub>)(TC-6,6)]
complex was structurally and spectroscopically characterized from
the reaction mixture. The {Co(NO)<sub>2</sub>}<sup>10</sup> species
was assigned
as the bis(cobalt dinitrosyl) complex [Co<sub>2</sub>(NO)<sub>4</sub>(TC-6,6)] by spectroscopic comparison with independently synthesized
and characterized material. These results provide the first evidence
for the influence of tropocoronand ring size on the nitric oxide reactivity
of the cobalt(II) complexes