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Rh(III) complexes of singly and doubly reduced phthalocyanine ligands generated by chemical and electrochemical reduction

Chemical Technology Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA

Corresponding author, Chemical Technology Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA.

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R. J. KLINGLER

Chemical Technology Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA

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J. W. RATHKE

Chemical Technology Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA

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https://doi.org/10.1002/jpp.335Cited by:5 (Source: Crossref)

Abstract

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.

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