191223-90-2Relevant academic research and scientific papers
A new general method for selective β-polynitration of porphyrins; preparation and redox properties of Zn-porphyrins bearing one through to eight β-nitro substituents and X-ray structure of the first Zn β-pernitro porphyrin
Palacio,Mansuy-Mouries,Loire,Le Barch-Ozette,Leduc,Barkigia,Fajer,Battioni,Mansuy
, p. 1907 - 1908 (2000)
Selective β-polynitration of Zn-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin, Zn(TDCPP), is achieved by controlled titration with the HNO3-CF3SO3H-(CF3SO2)2O system, and affords a full series of Zn porphyrins bearing one through to eight β-nitro groups in high yield and exhibiting a wide range of reduction potentials (from -920 to +155 mV vs. SCE); an X-ray structure of the first reported β-pernitrated Zn porphyrin Zn(TDCPN8P)(EtOH)2·2EtOH confirms the synthetic methodology.
A new manganese-β-heptanitro-porphyrin with extreme redox potentials: Spectral, electrochemical and catalytic properties
Ozette, Karine,Battioni, Pierrette,Leduc, Philippe,Bartoli, Jean-Francois,Mansuy, Daniel
, p. 4 - 6 (2008/10/08)
Manganese tetra-(2.6-dichlorophenyl)-β-heptanitroporphyrin was prepared by selective heptanitration of Zn(TDCPP = tetra-(2.6-dichlorophenyl)porphyrin), demetallation of the resulting porphyrin and treatment with Mn(OAc)2. It exists as a high-spin Mn(II) complex and it is electrochemically oxidized to the corresponding Mn(III) complex which exhibits the highest redox potential reported so far for an Mn(III) porphyrin (+940 mV versus SCE). Moreover it acts as a three-electron reservoir after three successive, reversible reductions at potentials unusually high for such reactions (+43, -220 and -745 mV versus SCE). It is also a good catalyst for alkene epoxidation and alkane hydroxylation by PhIO which constitutes a non-classical behavior for an Mn(II) porphyrin.
