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

Chi-Ming Che; Clare Ho; Tai-Chu Lau

doi:10.1039/DT9910001901

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

Chi-Ming Che
, Clare Ho
, Tai-Chu Lau

Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal

72 Citations (Scopus)

Abstract

The synthesis and characterization of [Ru^II(terpy)(dcbipy)(H₂O)]²⁺ (terpy = 2,2′:6′,2″-terpyridine; dcbipy = 6,6′-dichloro-2,2′-bipyridine) are described. Oxidation of this complex with Ce^IV gave [Ru^IV(terpy)(dcbipy)O]²⁺, isolated as a greenish yellow perchlorate salt. The Ru^IV=O complex is paramagnetic (μ_eff = 2.83) and exhibits a Ru=O stretch at 780 cm^-1. It is a powerful oxidant with E°(Ru^IV-Ru^III) = 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 Ru^IV=O has been investigated and discussed. The complex [Ru^II(terpy)(dcbipy)(H₂O)]²⁺ is a robust catalyst for the oxidation of saturated alkanes by tert-butyl hydroperoxide.

Original language	English
Pages (from-to)	1901-1907
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	8
DOIs	https://doi.org/10.1039/DT9910001901
Publication status	Published - 1991
Externally published	Yes

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title = "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=O complex is paramagnetic (μeff = 2.83) and exhibits a Ru=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=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.",

author = "Chi-Ming Che and Clare Ho and Tai-Chu Lau",

year = "1991",

doi = "10.1039/DT9910001901",

language = "English",

pages = "1901--1907",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "8",

}

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. / Che, Chi-Ming; Ho, Clare; Lau, Tai-Chu.
In: Journal of the Chemical Society, Dalton Transactions, No. 8, 1991, p. 1901-1907.

Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal

TY - JOUR

T1 - 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

AU - Che, Chi-Ming

AU - Ho, Clare

AU - Lau, Tai-Chu

PY - 1991

Y1 - 1991

N2 - 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=O complex is paramagnetic (μeff = 2.83) and exhibits a Ru=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=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.

AB - 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=O complex is paramagnetic (μeff = 2.83) and exhibits a Ru=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=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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U2 - 10.1039/DT9910001901

DO - 10.1039/DT9910001901

M3 - RGC 22 - Publication in policy or professional journal

SN - 1470-479X

SP - 1901

EP - 1907

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 8

ER -

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

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