Steric effect for proton, hydrogen-atom, and hydride transfer reactions with geometric isomers of NADH-model ruthenium complexes

Faraday Discuss. 2012:155:129-44; discussion 207-22. doi: 10.1039/c1fd00094b.

Abstract

Two isomers, [Ru(1)]2+ (Ru = Ru(bpy)2, bpy = 2,2'-bipyridine, 1 = 2-(pyrid-2'-yl)-1-azaacridine) and [Ru(2)]2+ (2 = 3-(pyrid-2'-yl)-4-azaacridine), are bioinspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C1 complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]2+ and [Ru(2)]2+ have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]2+ and [Ru(2HH)]2+, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2*-)] in aprotic and even protic media is slow compared to that of [Ru(1*-)]+. The net hydrogen-atom transfer between *[Ru(1)]2+ and hydroquinone (H2Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]2+ because the non-coordinated N atom is not easily available for an interaction with H2Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]2+ to [Ph3C]+ is significantly slower than that of [Ru (2HH)]2+ owing to steric congestion at the donor site.

Publication types

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

MeSH terms

  • 2,2'-Dipyridyl / chemistry
  • Acridines / chemistry
  • Coordination Complexes / chemistry
  • Electron Transport
  • Hydrogen / chemistry*
  • Hydroquinones / chemistry
  • Models, Molecular
  • NAD / chemistry*
  • NAD / metabolism
  • Nitrogen / chemistry
  • Photochemistry*
  • Protons*
  • Ruthenium / chemistry*
  • Water / chemistry*
  • Water / metabolism

Substances

  • Acridines
  • Coordination Complexes
  • Hydroquinones
  • Protons
  • Water
  • NAD
  • 2,2'-Dipyridyl
  • Ruthenium
  • Hydrogen
  • Nitrogen
  • hydroquinone