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Synthesis and spectroscopic characterization of bis-pocket porphyrins: Tetrakis(2,6-dinitrophenyl)porphyrin and catalytic activity of a manganese(III) chloride derivative in alkane oxidation

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00317a006· OSTI ID:7246191
; ;  [1]
  1. Sandia National Labs., Albuquerque, NM (USA)

The synthesis of tetrakis(2,6-dinitrophenyl)porphyrin (TDNPP) and tetrakis(2,6-diaminophenyl)porphyrin (TDAPP) has been achieved by modifying the Lindsey method as described. The new porphyrins serve as percursors for the synthesis of bis-deep-pocket metalloporphyrins that have completely enclosed, but dynamically accessible, cavities located adjacent to the central metal core on both faces of the macrocycle. Proton nuclear magnetic resonance spectroscopy of TDNPP shows that the porphyrin is substituted at the two phenyl positions ortho to the methine bridge carbon of the porphyrin. Fourier transform infrared spectroscopy demonstrates that the ortho substituents of the phenyl rings are in fact NO{sub 2} groups for TDNPP and NH{sub 2} groups for TDAPP. The manganese(III) chloride derivative of TDNPP was also synthesized and characterized by uv-visible absorption and resonance Raman spectroscopy. The Mn derivative was found to catalyze the hydroxylation of alkanes by using iodosylbenzene as the oxidant. 42 refs., 6 figs.

DOE Contract Number:
AC04-76DP00789
OSTI ID:
7246191
Journal Information:
Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:18; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English