Oxidation of Nitrite by a trans-Dioxoruthenium(VI) Complex : Direct Evidence for Reversible Oxygen Atom Transfer

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Wai-Lun Man
  • William W. Y. Lam
  • Wai-Yeung Wong
  • Tai-Chu Lau

Detail(s)

Original languageEnglish
Pages (from-to)14669-14675
Journal / PublicationJournal of the American Chemical Society
Volume128
Issue number45
Online published26 Oct 2006
Publication statusPublished - 15 Nov 2006

Abstract

Reaction of trans-[RuVI(L)(O)2]2+ (1, L = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane, a tetradentate macrocyclic ligand with N2O2 donor atoms) with nitrite in aqueous solution or in H2O/CH3CN produces the corresponding (nitrato)oxoruthenium(IV) species, trans-[Ru IV(L)(O)(ONO2)]+ (2), which then undergoes relatively slow aquation to give trans-[RuIV(L)(O)(OH2)]2+. These processes have been monitored by both ESI/MS and UV/vis spectrophotometry. The structure of trans-[RuIV(L)(O) (ONO2)]+ (2) has been determined by X-ray crystallography. The ruthenium center adopts a distorted octahedral geometry with the oxo and the nitrato ligands trans to each other. The Ru=O distance is 1.735(3) Å, the Ru-ONO2 distance is 2.163(4) Å, and the Ru-O-NO2 angle is 138.46(35)°. Reaction of trans-[RuVI(L)-(18O)2]2+ (1-18O2) with N16O2- in H2O/CH3CN produces the 18O-enriched (nitrato)oxoruthenium(IV) species 2- 18O2. Analysis of the ESI/MS spectrum of 2-18O2 suggests that scrambling of the 18O atoms has occurred. A mechanism that involves linkage isomerization of the nitrato ligand and reversible oxygen atom transfer is proposed.

Citation Format(s)

Oxidation of Nitrite by a trans-Dioxoruthenium(VI) Complex: Direct Evidence for Reversible Oxygen Atom Transfer. / Man, Wai-Lun; Lam, William W. Y.; Wong, Wai-Yeung et al.
In: Journal of the American Chemical Society, Vol. 128, No. 45, 15.11.2006, p. 14669-14675.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review