Iron complexes of new hydrophobic derivatives of tris(2-pyridylmethyl)amine: synthesis, characterization, and catalysis of alkane oxygenation by H2O2

Gregorio Guisado-Barrios, Alexandra M. Z. Slawin, David T. Richens

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5 Citations (Scopus)

Abstract

Several new iron(II) triflate complexes of 6-py-substituted derivatives of tris(2-pyridylmethyl)amine (TPA); [Fe(3-6)(CH3CN)(x)](CF3SO3)(2) (3 = tris-(6-methoxymethyl-2-pyridylmethyl)amine, x = 0; 4 = tris-(6-octoxymethyl-2-pyridylmethyl)amine, x = 0; 5 = 6-(N'-hexylureido-2-pyridylmethyl)-bis(2-pyridylmethyl)amine, x = 1; and 6 = bis-(6-(N'-hexylureido)-2-pyridylmethyl)-2-pyridylmethylamine) have been synthesized to probe the introduction of a hydrophobic peralkyl chain (4-6) and hydrogen-bonding (from urea N-H) (4 and 5) on the selective catalysis of alkane oxygenation by H2O2 in CH3CN. For [Fe(6)](CF3SO3)(2), hexadentate coordination of iron involving the two urea carbonyls was confirmed by X-ray structural analysis. Despite this, [Fe(6)](CF3SO3)(2) exhibited the highest A/K ratio (3.3), yet seen for catalysis of H2O2 oxygenation of cyclohexane by an iron(II) complex of a bis(6-py)- or tris(6-py)-substituted TPA derivative. This has been tentatively attributed to a degree of O-O cleavage assistance within high spin seven-coordinate [Fe(6)OOH](2+) via urea N-H protonation of the departing "OH" leading to participation from oxo-iron(IV) or (V) intermediates. The lack of similar hydrogen-bonding assistance results in [Fe(6)OOBut](2+) being one of the most long-lived high spin peroxoiron(III) complexes yet synthesized (t(1/2) = 1.3 h at 298 K).

Original languageEnglish
Pages (from-to)2642-2658
Number of pages17
JournalJournal of Coordination Chemistry
Volume63
Issue number14-16
DOIs
Publication statusPublished - 2010

Keywords

  • Iron
  • Tris-(2-pyridylmethyl)amine
  • Alkane oxidation
  • Catalysis
  • VALENT NONHEME IRON
  • HYDROGEN-PEROXIDE
  • CIS-DIHYDROXYLATION
  • OLEFIN EPOXIDATION
  • HYDROXYL RADICALS
  • ACETIC-ACID
  • OXIDATION
  • LIGAND
  • AUTOXIDATION
  • HYDROCARBONS

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