Proton-induced reactivity of NO⁻ from a {CoNO}⁸ complex

J Am Chem Soc. 2014 Sep 10;136(36):12560-3. doi: 10.1021/ja5064444. Epub 2014 Aug 1.

Abstract

Research on the one-electron reduced analogue of NO, namely nitroxyl (HNO/NO(-)), has revealed distinguishing properties regarding its utility as a therapeutic. However, the fleeting nature of HNO requires the design of donor molecules. Metal nitrosyl (MNO) complexes could serve as potential HNO donors. The synthesis, spectroscopic/structural characterization, and HNO donor properties of a {CoNO}(8) complex in a pyrrole/imine ligand frame are reported. The {CoNO}(8) complex [Co(LN4(PhCl))(NO)] (1) does not react with established HNO targets such as Fe(III) hemes or Ph3P. However, in the presence of stoichiometric H(+) 1 behaves as an HNO donor. Complex 1 readily reacts with [Fe(TPP)Cl] or Ph3P to afford the {FeNO}(7) porphyrin or Ph3P═O/Ph3P═NH, respectively. In the absence of an HNO target, the {Co(NO)2}(10) dinitrosyl (3) is the end product. Complex 1 also reacts with O2 to yield the corresponding Co(III)-η(1)-ONO2 (2) nitrato analogue. This report is the first to suggest an HNO donor role for {CoNO}(8) with biotargets such as Fe(III)-porphyrins.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Cobalt / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Nitric Oxide / chemistry*
  • Nitrogen Oxides / chemistry*
  • Organometallic Compounds / chemistry*
  • Protons*

Substances

  • Nitrogen Oxides
  • Organometallic Compounds
  • Protons
  • Nitric Oxide
  • Cobalt
  • nitroxyl