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Nuclear magnetic resonance studies of the formation of tertiary alkyl complexes of iron(III) porphyrins and their reactions with dioxygen.
Autorzy
Rok wydania
1990
Czasopismo
Journal of the American Chemical Society
Numer woluminu
112
Strony
7382-7388
DOI
10.1021/ja00176a044
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Iron(III) complexes of tetra-(p-tolyl)porphyrin (TTPH2) with axial adamantyl (1-ad), camphane (4-cam), and zerz-butylv ligands have been prepared and characterized by NMR spectroscopy. These have typical properties for low-spin (S = 1 /2), five-coordinate complexes. Analyses of the paramagnetic NMR spectral patterns for a variety of axial ligands are made and compared with those of aliphatic amines. These spectra exhibit sizeable dipolar shifts and can show non-Curie temperature dependence, particularly for the ^-protons. Treatment of TTPFem(4-cam), TTPFem(l-ad), or TTPFem(r-Bu) with dioxygen in toluene at -70 °C produces a mixture of TTPFeM1OH, TTPFemOFelllTTP, and TTPFe,luOOR (R = Zerz-butyl, 4-cam, or 1-ad). The absence of hydrogen atoms in the -carbon of these tertiary alkyl peroxide complexes alters their reactivity so that an intermediate formed by the 0-0 bond-breaking step can be detected. Treatment of TTPFemOO(4-cam) with pyridineat -70 °C results in its conversion into TTPFelv=0 through homolysis of the 0-0 bond.
Adres publiczny
https://doi.org/10.1021/ja00176a044
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