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ChemComm
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DOI: 10.1039/C6CC05440D
COMMUNICATION
Journal Name
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of the two MeCN ligands) thus regenerating the tetrahedral
[RuO4]- precursor. In contrast, pyridine N-oxide does not
regenerate [RuO4]- on voltammetric timescales. This is
consistent with the experimentally observed behavior by
Sharpless1 when this co-oxidant was employed and
demonstrates the superior reactivity of NMO in regenerating
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RuVII
.
In conclusion, cyclic voltammetry of [RuO4]- has defined
each of the ruthenium oxidation states involved in the
oxidative cycle, and those leading to catalyst decomposition.
Furthermore, CV determined which oxidation states are
sensitive to the presence of NMO, highlighting that NMO acts
as a two electron (O-atom transfer) co-oxidant converting RuV
to [RuO4]-. Overall, these observations have made a significant
advance in elucidating the mechanism for the Sharpless and
Griffith-Ley oxidations, which underpin future rational
development of next-generation oxidation protocols.
P.V.B. is grateful for financial support from the Australian
Research Council (DP150103345 and DP150104672). C.M.W.
also acknowledges the Australian Research Council for a
Future Fellowship (FT110100851) and a Discovery Projects
grant (DP160102887). T.J.Z. and P.W.M. are grateful for
Australian Post-graduate Awards.
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