1,1-Diamino-2,2-dintroethene (FOX-7) in copper and nickel diamine complexes and copper FOX-7

Abstract

1,1-Diamino-2,2-dinitroethene (FOX-7) reacts readily with copper nitrate in an aqueous solution of potassium hydroxide to form pea green Cu(FOX) 2(H 2O) 2 (5). FOX-7 complexes of copper and nickel supported by a variety of diamines including Cu(en) 2(FOX) 2(H 2O) (1), Cu(pn) 2(FOX) 2 (2), Cu(bipy)(FOX) 2(H 2O) 4 (3a), Cu(bipy) 2(FOX) 2(H 2O) 2.5 (3b), Cu(bipy)(FOX) 2(DMSO) 2•2DMSO (3c), Cu(phen) 3(FOX) 2(H 2O) 3 (4), (Ni) 2(phen) 6(FOX) 4(NO 3) 3(H 2O) 2 (6), and Ni(bipy) 3(FOX) 2(H 2O) 4 (7a) were obtained via metathesis reactions with potassium-FOX (K-FOX). Surprisingly FOX-7, in the presence of Ni(II) and bipyridyl in a mixed solvent of methanol and dimethyl sulfoxide, gave a chelated FOX carbamate anion resulting in the compound Ni(bipy) 2(FOX-CO 2)•(DMSO) (7b). All metal salts were characterized by infrared, elemental analysis, and differential scanning calorimetry (DSC). Single-crystal X-ray diffraction structures were obtained for compounds 1, 2, 3c, 6, and 7b. © 2012 American Chemical Society.