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Issue 1, 2004
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Synthesis, characterization and molecular structures of six-coordinate manganese nitrosyl porphyrins

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Abstract

Manganese(II) porphyrins are isoelectronic with iron(III) porphyrins, and previously reported work suggests that manganese nitrosyl porphyrins are good structural models for their kinetically unstable and biologically relevant ferric–NO analogues. We have prepared a new set of six-coordinate manganese nitrosyl porphyrins of the general form (por)Mn(NO)(L) (por = TTP, T(p-OCH3)PP; L = piperidine, methanol, 1-methylimidazole) in moderate to high yields. The (por)Mn(NO)(pip) complexes were prepared from the reductive nitrosylation of the (por)MnCl compounds with NO in the presence of piperidine. The IR spectra of the (por)Mn(NO)(pip) compounds as KBr pellets show new strong bands at 1746 cm−1 (for TTP) and 1748 cm−1 (for (T(p-OCH3)PP) due to the NO ligands. Attempted crystallization of one of these compounds (por = TTP) from dichloromethanemethanol resulted in the generation of the methanol complex (TTP)Mn(NO)(CH3OH). Reaction of the (por)Mn(NO)(pip) compounds with excess 1-methylimidazole gave the (por)Mn(NO)(1-MeIm) derivatives in good yields. The IR spectra of these compounds show νNO bands that are ∼12 cm−1 lower than those of the (por)Mn(NO)(pip) precursors, indicative of greater Mn→NO π-backdonation in the 1-MeIm derivatives. X-Ray crystal structures of three of these compounds, namely (TTP)Mn(NO)(CH3OH), (TTP)Mn(NO)(1-MeIm) and (T(p-OCH3)PP)Mn(NO)(1-MeIm) were obtained, and reveal that the NO ligands in these complexes are linear.

Graphical abstract: Synthesis, characterization and molecular structures of six-coordinate manganese nitrosyl porphyrins

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Publication details

The article was received on 16 Jul 2003, accepted on 23 Oct 2003 and first published on 14 Nov 2003


Article type: Paper
DOI: 10.1039/B308143P
Citation: Dalton Trans., 2004,0, 44-50
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    Synthesis, characterization and molecular structures of six-coordinate manganese nitrosyl porphyrins

    Z. N. Zahran, J. Lee, S. S. Alguindigue, M. A. Khan and G. B. Richter-Addo, Dalton Trans., 2004, 0, 44
    DOI: 10.1039/B308143P

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