82281-71-8Relevant academic research and scientific papers
Iron Porphyrin-Nitrene Complexes: Preparation from 1,1-Dialkylhydrazines. Electronic Structure from NMR, Moessbauer, and Magnetic Susceptibility Studies and Crystal Structure of the iron Complex
Mahy, Jean-Pierre,Battioni, Pierrette,Mansuy, Daniel,Fischer, Jean,Weiss, Raymond,et al.
, p. 1699 - 1706 (1984)
Iron(II) porphyrins (porphyrin = P = TPP, TTP and TpClPP) react with 1-amino-2,2,6,6-tetramethylpiperidine, in the presence of either dioxygen or one equivalent of iodosobenzene, to give the corresponding pentacoordinate nitrene complexes Fe(P)(NNC9H18) (P = TPP, 3a; P = TTP, 3b; P = TpClPP, 3c).These complexes, which are also formed by reaction of the iron(II) porphyrins with the free nitrene NNC9H18 at -80 deg C in CH2Cl2, have been isolated as pure crystalline solids in high yields.The structure of complex 3c has been fully established by an X-ray structure analysis; it is a pentacoordinate complex with the NNC9H18 nitrene as the axial ligand.Its Fe-N-N sequence is linear, and its Fe-N (1.809 angstroem) and N-N (1.232 angstroem) bonds have multiple bond character.It exhibits a marked doming of the porphyrin ring with the iron atom lying 0.54 angstroem above the mean plane of the porphyrin atoms.Magnetic susceptibility measurements on crystalline complex 3a (from 100 to 300 K) or on its solution in CDCl3 (307 K) lead to a magnetic moment of 5.1 +/- 0.1 μB. 1H and 13C NMR and Moessbauer studies on complex 3a are also in favor of a well-defined high-spin ferrous (S = 2) state for this complex.
