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

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

doi:10.1021/ja064975g

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

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

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

22 Citations (Scopus)

Abstract

Reaction of trans-[Ru^VI(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-[Ru^IV(L)(O)(OH₂)]²⁺. These processes have been monitored by both ESI/MS and UV/vis spectrophotometry. The structure of trans-[Ru^IV(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-[Ru^VI(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.

Original language	English
Pages (from-to)	14669-14675
Journal	Journal of the American Chemical Society
Volume	128
Issue number	45
Online published	26 Oct 2006
DOIs	https://doi.org/10.1021/ja064975g
Publication status	Published - 15 Nov 2006

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@article{08a6258c59bf4783a45f76242890472d,

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

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) {\AA}, the Ru-ONO2 distance is 2.163(4) {\AA}, 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.",

author = "Wai-Lun Man and Lam, \{William W. Y.\} and Wai-Yeung Wong and Tai-Chu Lau",

year = "2006",

month = nov,

day = "15",

doi = "10.1021/ja064975g",

language = "English",

volume = "128",

pages = "14669--14675",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "45",

}

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 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Oxidation of Nitrite by a trans-Dioxoruthenium(VI) Complex

T2 - Direct Evidence for Reversible Oxygen Atom Transfer

AU - Man, Wai-Lun

AU - Lam, William W. Y.

AU - Wong, Wai-Yeung

AU - Lau, Tai-Chu

PY - 2006/11/15

Y1 - 2006/11/15

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/33751013732

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-33751013732&origin=recordpage

U2 - 10.1021/ja064975g

DO - 10.1021/ja064975g

M3 - RGC 21 - Publication in refereed journal

C2 - 17090053

SN - 0002-7863

VL - 128

SP - 14669

EP - 14675

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 45

ER -

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

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