Spectroelectrochemical and DFT Evidence for Separate Electron Transfer Sites in an Iron Nitrosyl Complex of a Strongly Electron Accepting Porphyrin Ligand

PELLEGRINO, J.; HÜBNER, R.; DOCTOROVICH, F.; KAIM, W

CHEMISTRY-A EUROPEAN JOURNAL

WILEY-V C H VERLAG GMBH

Lugar: Weinheim; Año: 2011 vol. 17 p. 7868 - 7874

0947-6539

Abstract: Experimental and computational results for the electron-deficientporphyrin complex (1; TFPPBr8= 2,3,7,8,12,13,17,18-octabromo- 5,10,15,20- tetrakis(pentafluorophenyl)- porphyrin) are reported with respect to its electron-transfer behavior. Complex 1 undergoes three one-electron processes: two reversible reductions andone irreversible oxidation. Spectroelectrochemical measurements (IR and UV/Vis/NIR spectroscopy) of 14NO and 15NO-containing material indicate that the first reduction to 1 occurs largely on the NO ligand to produce nitroxyl anion (NO) character, as evidentfrom the considerable change in nNO from 1715 to around 1550 cm1.