Darstellung, Eigenschaften und elektronische Raman-Spektren von Di(bromo)phthalocyaninatometallaten(III) der Eisengruppe / Synthesis, Properties and Electronic Raman Spectra of Di(bromo)phthalocyaninatometalates(III) of the Iron Group Elements

Abstract

Abstract Low spin di(bromo)phthalocyaninatometalates of tervalent iron, ruthenium and osmium ([MBr 2 Pc 2- ] - ) are formed by the reaction of [FeBrPc 2- ] or H[MBr 2 Pc 2- ] (M = Ru, Os) with excess bromide in DMF or THF and isolated as ( n Bu 4 N) + salts. The electronic spectra show the typical π- π*- transitions (B, Q, N region) of the Pc 2- ligand together with a number of extra bands due to trip-multiplett and (Pc, Br → M)CT transitions. ν s (MBr) is observed in the resonance Raman (RR) spectrum (RR enhanced for M = Fe, Ru) at 161 cm -1 (Fe), 183 cm -1 (Ru) and 192 cm -1 (Os), ν as (MBr) at 251 cm -1 (Fe), 234 cm -1 (Ru) and 218 cm-1 (Os) in the FIR spectra. The RR spectra obtained by excitation at low absorbance between the B and Q region are dominated by the intraconfigurational " Γ 7 →Γ 8" transition due to spin orbit splitting of the 2 T 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 Os complex.