Highly Variable π-Bonding in the Interaction of Iron(II) Porphyrinates with Nitrite
| Autor: | W. Robert Scheidt, Carsten Krebs, Mary K. Ellison, Habib Nasri, and Boi Hanh Huynh |
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| Rok vydání: | 2000 |
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| Zdroj: | Journal of the American Chemical Society. 122:10795-10804 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja000149a |
| Popis: | The reaction of the four-coordinate picket fence iron(II) porphyrin complex [Fe(TpivPP)] with cryptand-solubilized KNO2 yields the five-coordinate porphyrin species [Fe(TpivPP)(NO2)]-. The six-coordinate complexes, [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]-, are obtained when pentamethylene sulfide or pyridine is added anaerobically to the preformed five-coordinate porphyrin species. These novel species are characterized by UV−vis, IR, and Mossbauer spectroscopies as well as single-crystal structure determinations. The Mossbauer investigation shows that the isomer shifts and quadrupole splittings for [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- are typical for six-coordinate, low-spin (S = 0) iron(II) porphyrinate complexes. This is in distinct contrast to the unusually large quadrupole splitting of the five-coordinate species [Fe(TpivPP)(NO2)]-. The molecular structures of [Fe(TpivPP)(NO2)(PMS)]- and [Fe(TpivPP)(NO2)(Py)]- show that the nitro groups are inside the “pocket” of the porphyrin ... |
| Databáze: | OpenAIRE |
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