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

Autor: Michael J. Chen, R. J. Klingler, Jerome W. Rathke
Rok vydání: 2001
Předmět:
Zdroj: Journal of Porphyrins and Phthalocyanines. :442-448
ISSN: 1099-1409
1088-4246
DOI: 10.1002/jpp.335
Popis: The paramagnetic complexes ( FPc )( Me ) Rh - (4) and (FPc)( PMe 3)( Me ) Rh - (10) have been prepared by reducing ( FPc )( Me ) Rh (1) and ( FPc )( PMe 3)( Me ) Rh (2) with NaBH 4 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 NaBH 4 to complexes, which are assigned to ( DFPc )( Me ) Rh - (5) and ( DFPc )( PMe 3)( Me ) Rh - (11), respectively. Based on the 1 H 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.
Databáze: OpenAIRE
Externí odkaz: