Narrow Results

The paramagnetic complexes (FPc)(Me)Rh^- (4) and (FPc)(PMe₃)(Me)Rh^- (10) have been prepared by reducing (FPc)(Me)Rh (1) and (FPc)(PMe₃)(Me)Rh (2) with NaBH₄ in methanol-d₄ [FPc^2- = dianion of 1,4,8,11,15,18,22,25-octakis(trifluoromethyl)phthalocyanine]. Compounds 4 and 10 are further reduced by NaBH₄ to complexes, which are assigned to (DFPc)(Me)Rh^- (5) and (DFPc)(PMe₃)(Me)Rh^- (11), respectively. Based on the ¹H NMR spectra of these complexes, 4 and 10 are assigned to the Rh(III) complexes of the singly reduced radical anion FPc^·3-, while 5 and 11 are assigned to the Rh(III) complexes of the doubly reduced, antiaromatic anion DFPc^3-, which has the deuteron bonded to one of its meso nitrogens. As expected, the antiaromatic complexes 5 and 11 are not stable. At -40 °C, 5 was transformed successively into three aromatic compounds, the first of which was assigned to the ring-contracted α,β,γ-triazatetrabenzocorrole complex (TBC)(Me)Rh^- [TBC^3- = trianion of 3,6,10,13,17,20,24,27-octakis(trifluoromethyl)-α,β,γ-triazatetrabenzocorrole]. Cyclic voltammetry of 1 and 2 was also carried out. Two reversible one-electron reduction waves were observed for both 1 and 2.