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Oxidation of Organic Substrates with RuIV=O Complexes Formed by Proton-Coupled Electron Transfer.

Oxidation of Organic Substrates with RuIV=O Complexes Formed by Proton-Coupled Electron Transfer.

Authors :
Tomoya Ishizuka
Shingo Ohzu
Takahiko Kojima
Source :
Synlett; 2014, Vol. 25 Issue 12, p1667-1679, 13p
Publication Year :
2014

Abstract

We describe our recent progress in mechanistic investigations on substrate oxidation reactions with Ru<superscript>IV</superscript>=O complexes having pyridylamine ligands. The Ru<superscript>IV</superscript>=O complexes are synthesized from the corresponding Ru<superscript>II</superscript>-OH<subscript>2</subscript> complexes either through a proton-coupled electron-transfer procedure using a cerium(IV) complex as an oxidant or by bulk electrolysis. We have verified the presence of an adduct-formation equilibrium between the Ru<superscript>IV</superscript>=O complex and a substrate in water, which strongly affects the reaction mechanism of the substrate oxidation. We have also shown that the reaction rates of the substrate oxidation in water are independent of the spin states of the RuIV centers and of the bond-dissociation enthalpy of the C-H bond of the substrate. Additionally, we have applied the Ru<superscript>II</superscript>-OH<subscript>2</subscript> complexes as catalysts for photocatalytic substrate oxidations and have observed very efficient catalytic activity. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
09365214
Volume :
25
Issue :
12
Database :
Complementary Index
Journal :
Synlett
Publication Type :
Academic Journal
Accession number :
97124764
Full Text :
https://doi.org/10.1055/s-0033-1341018