PREPARATION AND CHARACTERIZATION OF CHROMIUM(V)-NITRIDOPHTHALOCYANINES AND MANGANESE(V)-NITRIDOPHTHALOCYANINES(1-) AND MAGANESE(V)-NITRIDOPHTHTHALOCYANINES-[MNPC(1-)]+ AND [MNPC(2-)] (M=CR, MN)

Nitridophthalocyaninatochromium(V), [CrNPc(2-)], is prepared by oxidation of [Cr(OH)2Pc(2-)]- with chlorine in the presence of excess ammonia as a paramagnetic (mu(eff) = 1,99 B.M.), micro-crystalline blue powder. Through chemically very stable it reacts as well as the isostructural nitridophthalocyaninatomanganese(V) with bromine or concentrated nitric acid giving ring-oxidized dark blue nitridophthalocyaninatometal(poly)bromides or -nitrates, [MNPc(1-)]X(M = Cr, Mn; X = Br(y), NO3; y almost-equal-to 2). The nitrido-metal stretching vibration (nu(N = M)) is independent of the oxidation state of the Pc-ligands at ca. 1 017 cm-1 for the chromium- and at ca. 1 055 cm-1 for the manganesenitridophthalocyanines. Nu(N = Mn) is resonance Raman (rr.) enhanced, nu(N = Cr) not. The characteristic differences in the u.v.-vis., f.i.r./m.i.r. and r.r. spectra of [MNPc(2-)] and [MNPc(1-)]+ and the influence of aggregation of phthalocyanine-radicals are discussed.