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Issue 8, 1991
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Tuning the reactivities of ruthenium–oxo complexes with robust ligands. A ruthenium(IV)–oxo complex of 6,6′-dichloro-2,2′-bipyridine as an active oxidant for stoichiometric and catalytic organic oxidation

Abstract

The synthesis and characterization of [RuII(terpy)(dcbipy)(H2O)]2+(terpy = 2,2′:6′,2″-terpyridine; dcbipy = 6,6′-dichloro-2,2′-bipyridine) are described. Oxidation of this complex with CeIV gave [RuIV(terpy)(dcbipy)O]2+, isolated as a greenish yellow perchlorate salt. The RuIV[double bond, length half m-dash]O complex is paramagnetic (µeff= 2.83) and exhibits a Ru[double bond, length half m-dash]O stretch at 780 cm–1. It is a powerful oxidant with E°(RuIV–RuIII)= 1.13 V vs. saturated calomel electrode at pH 1.0 and can selectively oxidize the tertiary C–H bond of adamantane. The mechanism of alkene oxidation by RuIV[double bond, length half m-dash]O has been investigated and discussed. The complex [RuII(terpy)(dcbipy)(H2O)]2+ is a robust catalyst for the oxidation of saturated alkanes by tert-butyl hydroperoxide.

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Article type: Paper
DOI: 10.1039/DT9910001901
Citation: J. Chem. Soc., Dalton Trans., 1991,0, 1901-1907

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    Tuning the reactivities of ruthenium–oxo complexes with robust ligands. A ruthenium(IV)–oxo complex of 6,6′-dichloro-2,2′-bipyridine as an active oxidant for stoichiometric and catalytic organic oxidation

    C. Che, C. Ho and T. Lau, J. Chem. Soc., Dalton Trans., 1991, 0, 1901
    DOI: 10.1039/DT9910001901

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