Variable Nitric Oxide Reactivity of Tropocoronand Cobalt(III) Nitrite Complexes as a Function of the Polymethylene Linker Chain Length
2012-09-03T00:00:00Z (GMT) by
The size-dependent reactivity of cobalt tropocoronands [TC-n,n]2– is manifest in the NO chemistry of the cobalt(III) nitrite complexes [Co(η2-NO2)(TC-n,n)] (n = 4–6), the synthesis and characterization of which are reported for the first time. Complete conversion of [Co(η2-NO2)(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(η2-NO2)(TC-5,5)] generates both cobalt mono- and dinitrosyl adducts, and addition of nitric oxide to [Co(η2-NO2)(TC-6,6)] converts this complex to the dicobalt tetranitrosyl species [Co2(NO)4(TC-6,6)]. In the latter complex, two tetrahedral cobalt dinitrosyl units are bound to the aminotroponeiminate poles of the [TC-6,6]2– ligand. These results significantly broaden the chemistry of cobalt tropocoronands with nitric oxide and the nitrite anion.
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