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.
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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 -