Variable Nitric Oxide
Reactivity of Tropocoronand
Cobalt(III) Nitrite Complexes as a Function of the Polymethylene Linker
Chain Length
Julia Kozhukh
Stephen J. Lippard
10.1021/ic3012266.s001
https://acs.figshare.com/articles/journal_contribution/Variable_Nitric_Oxide_Reactivity_of_Tropocoronand_Cobalt_III_Nitrite_Complexes_as_a_Function_of_the_Polymethylene_Linker_Chain_Length/2491696
The size-dependent reactivity of cobalt tropocoronands
[TC-<i>n</i>,<i>n</i>]<sup>2–</sup> is
manifest in
the NO chemistry of the cobalt(III) nitrite complexes [Co(η<sup>2</sup>-NO<sub>2</sub>)(TC-<i>n</i>,<i>n</i>)]
(<i>n</i> = 4–6), the synthesis and characterization
of which are reported for the first time. Complete conversion of [Co(η<sup>2</sup>-NO<sub>2</sub>)(TC-4,4)] to the cobalt mononitrosyl [Co(NO)(TC-4,4)]
occurs upon exposure to NO(g). In contrast, addition of NO(g) to [Co(η<sup>2</sup>-NO<sub>2</sub>)(TC-5,5)] generates both cobalt mono- and
dinitrosyl adducts, and addition of nitric oxide to [Co(η<sup>2</sup>-NO<sub>2</sub>)(TC-6,6)] converts this complex to the dicobalt
tetranitrosyl species [Co<sub>2</sub>(NO)<sub>4</sub>(TC-6,6)]. In
the latter complex, two tetrahedral cobalt dinitrosyl units are bound
to the aminotroponeiminate poles of the [TC-6,6]<sup>2–</sup> ligand. These results significantly broaden the chemistry of cobalt
tropocoronands with nitric oxide and the nitrite anion.
2012-09-03 00:00:00
tetrahedral cobalt dinitrosyl units
dicobalt tetranitrosyl species
Variable Nitric Oxide Reactivity
TC
cobalt tropocoronands
nitric oxide
Co