PHTHALOCYANINES OF COBALT AND RHODIUM WIT H O, S, AND SE DONOR LIGANDS

Di(phenolato)-, -(benzenethiolato)- and -(benzeneselenonato)phthalocya ninatocobaltate(III) and -rhodate(III) are prepared by the reaction of di(hydroxo)phthalocyaninatometalate with phenol resp. benzenethiol or benzeneselenol and isolated as poorly soluble tetra(n-butyl)ammonium salts of the formula (nBu4N)[M(EPh)2Pc2-] (M = Co, Rh; E = 0, S, Se). In the Uv-vis spectra pi-pi transitions in the Pc2 -typical B, Q, N a nd L regions are observed. For the Rh-complexes with E = S, Se there i s a further band at 18.0 kK due to excitonic pi(Ph)-pi(Pc) interaction s. The (E-->Rh-charge-transfer(CT)) transition is observed for E = Se at 26.0 kK, being obscured by the Q, N region for E = O, S. The strong , broad (E-Co-CT) transition (E = O, S, Se) absorbs at - 20.5 kK. A se cond CT-transition is detected within the Q, N region for E = S, Se. M olecular vibrations (in cm-1) are examined by m.i.r., f.i.r, FT-Raman and dispersive resonance-Raman(RR) spectra. The C-E stretching mode (n u7a) of the axial EPh ligands is observed for E = O at 1256/1262, 1269 (Co, m.i.r./RR), 1246/1265 (Rh), for E = S at 1 085 (Co, Rh; RR) and for E = Se at 1 069 (Co, Rh; RR). The C-C-E deformation mode (nu6a) is assigned for E = 0 at 554/557 (Co, RR), 568 (Rh, RR) and for E = S at 420 (Co, Rh; RR). The following vibrational modes of the trans-ME2N4 skeleton are assigned: nu(s)(ME) for Co:381 (O)/271 (S)/139 (Se); for Rh:408/297/156; nu(as)(ME) for Co:352/277/235; for Rh:391/278/225; nu( as)(MN) absorbs nearly independent of M and E at -325 (f.i.r.). M-E-C deformation modes are observed between 246 and 200 (f.i.r.) resp. 217 and 186 (RR).