A nickel-containing model system of acireductone dioxygenases that utilizes a C(1)-H acireductone substrate

Caleb J. Allpress, Lisa M. Berreau

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

A mononuclear Ni<sup>II</sup> complex bearing the monoanion of 1-acetoxy-3-phenylpropane-2,3-dione (4) as a ligand has been prepared {[(6-Ph<inf>2</inf>TPA)Ni{PhC(O)C(O)CHOC(O)CH<inf>3</inf>)]ClO<inf>4</inf>, 5; 6-Ph<inf>2</inf>TPA = N,N-bis[(6-phenyl-2-pyridyl)methyl]-N-(2-pyridylmethyl)amine}. This complex was characterized by <sup>1</sup>H NMR, UV/Vis and IR spectroscopy, mass spectrometry, and elemental analysis. Exposure of solutions of 5 to O<inf>2</inf> did not result in any reaction over the course of hours. Deprotection of 5 by the addition of NaOCH<inf>3</inf> in methanol generated a Ni<sup>II</sup> species (6) that contains a coordinated dianionic C(1)-H acireductone. Exposure of 6 to O<inf>2</inf> led to regioselective oxidative cleavage reactivity akin to that found for the Ni<sup>II</sup>-containing acireductone dioxygenase enzyme. The strategy outlined herein is the first synthetic approach that enables examination of the oxidative reactivity of a synthetic Ni<sup>II</sup> species containing a dianionic C(1)-H acireductone ligand.

Original languageEnglish (US)
Pages (from-to)4642-4649
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2014
Issue number27
DOIs
StatePublished - Sep 1 2014

Keywords

  • Cleavage reactions
  • Enzyme mimics
  • Metalloenzymes
  • Nickel
  • Oxygen
  • Regioselectivity

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