Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex

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

doi:10.1039/DT9910001259

Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex

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

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

50 Citations (Scopus)

Abstract

The complex [Ru^vL(O)]²⁺ {HL = [2-hydroxy-2-(2-pyridyl)ethyl]bis[2-(2-pyridyl)ethyl]amine} was found to be a very active stoichiometric oxidant towards various hydrocarbons. Oxidation of alcohols was studied either in 0.1 mol dm^-3 HClO₄ or CH₃CN, the observed rate law being rate = k[Ru^v][alcohol]. The second-order rate constants for various alcohols follow the order benzylic > secondary > primary alcohols. Kinetic isotope effects (k_H/k_D) of 5.9 and 5.3 were found for benzyl alcohol and PrⁱOH respectively. Similar kinetic studies for the oxidation of tetrahydrofuran gave k_H/k_D = 6.8. Stoichiometric oxidation of saturated alkanes in acetonitrile gave tertiary alcohols exclusively or ketones when only methylene groups are present. The measured k_H/k_D for the oxidation of cyclohexane determined from competitive oxidation experiments was 5.3. No cyclohexyl chloride was found when the oxidation of cyclohexane was carried out in the presence of CCl₄. The mechanism of C-H bond oxidation by Ru^v=O is discussed.

Original language	English
Pages (from-to)	1259-1263
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	5
DOIs	https://doi.org/10.1039/DT9910001259
Publication status	Published - 1991
Externally published	Yes

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@article{6e0a8a7305e54fd3a2f617bfd33d7c19,

title = "Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex",

abstract = "The complex [RuvL(O)]2+ \{HL = [2-hydroxy-2-(2-pyridyl)ethyl]bis[2-(2-pyridyl)ethyl]amine\} was found to be a very active stoichiometric oxidant towards various hydrocarbons. Oxidation of alcohols was studied either in 0.1 mol dm-3 HClO4 or CH3CN, the observed rate law being rate = k[Ruv][alcohol]. The second-order rate constants for various alcohols follow the order benzylic > secondary > primary alcohols. Kinetic isotope effects (kH/kD) of 5.9 and 5.3 were found for benzyl alcohol and PriOH respectively. Similar kinetic studies for the oxidation of tetrahydrofuran gave kH/kD = 6.8. Stoichiometric oxidation of saturated alkanes in acetonitrile gave tertiary alcohols exclusively or ketones when only methylene groups are present. The measured kH/kD for the oxidation of cyclohexane determined from competitive oxidation experiments was 5.3. No cyclohexyl chloride was found when the oxidation of cyclohexane was carried out in the presence of CCl4. The mechanism of C-H bond oxidation by Ruv=O is discussed.",

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

year = "1991",

doi = "10.1039/DT9910001259",

language = "English",

pages = "1259--1263",

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

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "5",

}

TY - JOUR

T1 - Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex

AU - Che, Chi-Ming

AU - Ho, Clare

AU - Lau, Tai-Chu

PY - 1991

Y1 - 1991

N2 - The complex [RuvL(O)]2+ {HL = [2-hydroxy-2-(2-pyridyl)ethyl]bis[2-(2-pyridyl)ethyl]amine} was found to be a very active stoichiometric oxidant towards various hydrocarbons. Oxidation of alcohols was studied either in 0.1 mol dm-3 HClO4 or CH3CN, the observed rate law being rate = k[Ruv][alcohol]. The second-order rate constants for various alcohols follow the order benzylic > secondary > primary alcohols. Kinetic isotope effects (kH/kD) of 5.9 and 5.3 were found for benzyl alcohol and PriOH respectively. Similar kinetic studies for the oxidation of tetrahydrofuran gave kH/kD = 6.8. Stoichiometric oxidation of saturated alkanes in acetonitrile gave tertiary alcohols exclusively or ketones when only methylene groups are present. The measured kH/kD for the oxidation of cyclohexane determined from competitive oxidation experiments was 5.3. No cyclohexyl chloride was found when the oxidation of cyclohexane was carried out in the presence of CCl4. The mechanism of C-H bond oxidation by Ruv=O is discussed.

AB - The complex [RuvL(O)]2+ {HL = [2-hydroxy-2-(2-pyridyl)ethyl]bis[2-(2-pyridyl)ethyl]amine} was found to be a very active stoichiometric oxidant towards various hydrocarbons. Oxidation of alcohols was studied either in 0.1 mol dm-3 HClO4 or CH3CN, the observed rate law being rate = k[Ruv][alcohol]. The second-order rate constants for various alcohols follow the order benzylic > secondary > primary alcohols. Kinetic isotope effects (kH/kD) of 5.9 and 5.3 were found for benzyl alcohol and PriOH respectively. Similar kinetic studies for the oxidation of tetrahydrofuran gave kH/kD = 6.8. Stoichiometric oxidation of saturated alkanes in acetonitrile gave tertiary alcohols exclusively or ketones when only methylene groups are present. The measured kH/kD for the oxidation of cyclohexane determined from competitive oxidation experiments was 5.3. No cyclohexyl chloride was found when the oxidation of cyclohexane was carried out in the presence of CCl4. The mechanism of C-H bond oxidation by Ruv=O is discussed.

UR - https://www.scopus.com/pages/publications/37049079516

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-37049079516&origin=recordpage

U2 - 10.1039/DT9910001259

DO - 10.1039/DT9910001259

M3 - RGC 22 - Publication in policy or professional journal

SN - 1470-479X

SP - 1259

EP - 1263

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 5

ER -

Mechanism of C-H bond oxidation by a monooxoruthenium(V) complex

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