Ruthenium oxo complexes as organic oxidants

Griffith, William P.

doi:10.1039/cs9922100179

Cited by 198 publications

(102 citation statements)

References 37 publications

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“…grade Merck). Ruthenium dioxide, diethyl ether, acrylonitrile, 2,4,6-tritertbutylphenol, and 2-propanol-d 6 were purchased from Aldrich Chemical Co. (A.R. grade).…”

Section: Methodsmentioning

confidence: 99%

“…The catalytic activity of these transition metals ions [1 -4] is generally attributed to their capacity to exist in more than one oxidation state, their capacity to form complexes with various organic compounds, and their capacity to change their coordination number [5]. Recently, the use of oxo-com- , and RuO 4 2Ϫ ) to effect catalytic homogeneous alcohol oxidations has become increasingly important because these catalytic species participate in such reactions without attacking sensitive linkages in the R group of the alcohol [6].…”

Section: Introductionmentioning

confidence: 99%

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Kinetic study of ruthenium(VI)-catalyzed oxidation of 2-butanol by alkaline hexacyanoferrate(III)

Mucientes

Poblete

Rodrı́guez

et al. 1999

Int. J. Chem. Kinet.

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The oxidation kinetics of 2-butanol by alkaline hexacyanoferrate(III) catalyzed by sodium ruthenate has been studied spectrophotometrically. The initial rates method was used for kinetic analysis. The reaction rate shows a fractional-order in [hexacyanoferrate(III)] and [substrate] and a first-order dependence on [Ru(VI)]. The dependence on [OH Ϫ ] is rather more complicated. The kinetic data suggest a reaction mechanism involving two active catalytic species. Each one of these species forms an intermediate complex with the substrate. The attack of these complexes by hexacyanoferrate(III), in a slow step, produces ruthenium(V) complexes which are oxidized in subsequent steps to regenerate the catalyst species.

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“…grade Merck). Ruthenium dioxide, diethyl ether, acrylonitrile, 2,4,6-tritertbutylphenol, and 2-propanol-d 6 were purchased from Aldrich Chemical Co. (A.R. grade).…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Kinetic study of ruthenium(VI)-catalyzed oxidation of 2-butanol by alkaline hexacyanoferrate(III)

Mucientes

Poblete

Rodrı́guez

et al. 1999

Int. J. Chem. Kinet.

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“…1 Traditionally, oxidation of alcohols is carried out using stoichiometric amounts of metallic oxidants notably chromium(VI) reagents, 2 permanganates, 3 and ruthenium(VIII) oxide, 4 which produce environmentally unacceptable heavy metal wastes.…”

Section: Introductionmentioning

confidence: 99%

A new metal-free protocol for oxidation of alcohols using TsNBr2 without catalyst

Phukan¹,

Chakraborty²,

Saikia³

2010

Arkivoc

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“…In a review published in 1992, Griffith calls attention to the fact that "the mechanism of oxidation by TPAP is not clear… and this aspect needs investigation". 239 A more recent volume published by the same author in 2013 indicates that little progress has been achieved in this regard. 243 The original high-valent ruthenium oxidising agent is the extremely reactive ruthenium tetroxide,…”

Section: Redox Potentials -Ementioning

confidence: 99%

“…The values of kIIa,X had a negligible effect on the fit of the voltammetry and can be found in Table 4.1 The Ley-Griffith oxidation, 3,30,[239][240][241][242] which is catalysed by tetra-n-propylammonium perruthenate (n-Pr4N[RuO4] or TPAP), is synonymous in this regard and has been adopted for the synthesis of an extensive array of fine chemicals, including pharmaceuticals and natural product targets.…”

Section: Halide Binding Constant -Kiixmentioning

confidence: 99%

Understanding the mechanisms of transition metal catalysed redox reactions

Zerk¹

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Transition metal complexes catalyse a number of important synthetic chemical reactions. Two such reactions which rely on copper and ruthenium complexes respectively are atom transfer radical polymerisation (ATRP) and the Ley-Griffith oxidation of alcohols.In ATRP a copper(I) complex bearing a chelate ligand 'L' homolytically cleaves the carbon-halogen bond of an organo halide initiator (R-X) to produce an alkyl radical and the corresponding copper(II)-halido complex (Cu I L + RX → R• + Cu II LX). The reverse reaction is coined 'deactivation' and provides control to the process by keeping the concentration of the radical low. It is experimentally difficult to determine the rate of this reaction because it is so fast. Herein, a new method for measuring the rate of deactivation is developed using cyclic voltammetry coupled to simulations. The mechanism of deactivation is also unknown and this aspect is investigated by a kinetic study of halide substitution reactions on three ATRP-relevant Cu ). EPR spectroscopy alsoshows that NMO forms an outer-sphere associated complex with perruthenate which may be important in facilitating this reaction. Finally, synergistic EPR and UV-vis spectroscopy demonstrate that even with a large excess of NMO, a small amount of ruthenium dioxide still forms during the Ley-Griffith oxidation and acts as an accelerant for the reaction -i.e. the reaction is auto-catalytic. Declaration by author

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Ruthenium oxo complexes as organic oxidants

Cited by 198 publications

References 37 publications

Kinetic study of ruthenium(VI)-catalyzed oxidation of 2-butanol by alkaline hexacyanoferrate(III)

Kinetic study of ruthenium(VI)-catalyzed oxidation of 2-butanol by alkaline hexacyanoferrate(III)

A new metal-free protocol for oxidation of alcohols using TsNBr2 without catalyst

Understanding the mechanisms of transition metal catalysed redox reactions

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