SYNTHESIS, PROPERTIES AND ELECTRONIC RAMA N-SPECTRA OF DI(BROMO)PHTHALOCYANINATOMETALATES(III) OF THE IRON-GROUP ELEMENTS

Low spin di(bromo)phthalocyaninatometalates of tervalent iron, rutheni um and osmium ([MBr(2)Pc(2-)](-)) are formed by the reaction of [FeBrP c(2-)] or H[MBr(2)Pc(2-)] (M = Ru, Os) with excess bromide in DMF or T HF and isolated as ((n)Bu(4)N)(+) salts. The electronic spectra show t he typical pi-pi-transitions (B, Q, N region) of the Pc(2-) ligand to gether with a number of extra bands due to trip-multiplett and (Pc, Br --> M)CT transitions, v(s)(MBr) is observed in the resonance Raman (R R) spectrum (RR enhanced for M = Fe, Ru) at 161 cm(-1) (Fe), 183 cm(-1 ) (Ru) and 192 cm(-1) (Os), v(as)(MBr) at 251 cm(-1) (Fe), 234 cm(-1) (Ru) and 218 cm(-1) (Os) in the FIR spectra. The RR spectra obtained b y excitation at low absorbance between the B and Q region are dominate d by the intraconfigurational ''Gamma(7) --> Gamma(8)'' transition due to spin orbit splitting of the 2T(2g) ground state for Fe at 583 cm(- 1), Ru at 1026/1050 cm(-1) and Os at 3131 cm(-1). In the MIR resp. NIR spectra vibronically induced transitions are observed for the Ru or O s complex.