Reaction of the Small-Ring Macrocycle N,N'–dimethyltribenzo–1,4,7–triazacyclononatriene and Copper(II) Bromide Produces Three Distinctly Different Products, Including a Nitrogen Cation Radical
Roberts, Madeleine G.
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This work began in 2010 as an attempt to form stable CuII complexes with a small ring organic macrocycle, N,N'–dimethyltribenzo–1,4,7–triazacyclononatriene (Me2N3—CTV) and copper(II) bromide (CuIIBr); instead the macrocycle reactant oxidized and rearranged to form a nitrogen cation radical and copper(I) anion in the recrystallization of the reaction solution, 5,9–dimethyl–5,9—dihydroquinoxalino–[3,2,1–de]phenazine ([Me2—DQPh]+). Previous work with X-ray crystallography and computational chemistry provided insight on the radical. The overnight reaction at room temperature of Me2N3—CTV and CuBr2 in methanol (MeOH) is now known to produce three main products, [Me2—DQPh]+[CuBr2]- in the form of a black solid that is orange in solution, a black solid that is green in solution, and an orange solid. Investigation into all reaction components, including a previously disregarded reaction precipitate, resulted in a new understanding of the products. Characterization of the complicated, but distinct electronic spectra of each component in the 200-900 nm range allowed for the development of a procedure to isolate the three main products from each other. The current study has accomplished a procedure to separate the three products, a beginning characterization of the three products using spectroscopy, and the direct production of the nitrogen cation radical compound from the synthetic reaction. Laboratory work continues to identify the two remaining products.