Oxidation of secondary alcohols byN-methylmorpholine-N-oxide (NMO) catalyzed by Ru(II) halosulfoxide complexes. A kinetic study

Tony, K. J.; Rajaram, J.; Mahadevan, V.; Swamy, C. S.

doi:10.1007/bf02477703

Cited by 5 publications

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References 17 publications

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“…The substitution processes are also important to another flourishing area of research that is supramolecular chemistry because Ru−Cl−DMSO complexes are used as building blocks to assemble complex 3D architectures . In the area of catalysis, [RuCl 2 (DMSO) 4 ] as well as other Ru−Cl−DMSO complexes containing other ligands, are particularly interesting as precursors and catalysts for a variety of reactions including hydrogen-atom transfer, hydrogenation, α-alkylation of ketones, aerobic oxidation of alcohols, oxidation of aliphatic ethers to esters, isomerization of alcohols, selective oxidation of aryl sulfides with molecular oxygen, etc.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Chemistry of Ru(II) Complexes Containing Cl and DMSO Ligands

et al. 2007

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Two new isomers trans,mer-[RuIICl2(bpea)(DMSO)], 2a, and cis,fac-[RuIICl2(bpea)(DMSO)], 2b, (bpea = N,N-bis(2-pyridylmethyl)ethylamine), as well as the bis-DMSO complex trans,fac-[RuIICl(bpea)(DMSO)2]Cl, 3, have been synthesized and characterized by cyclic voltammetry and UV-vis and 1D and 2D NMR spectroscopy in solution. Their solid-state structure has also been solved by means of single-crystal X-ray diffraction analysis. All the three complexes display a ruthenium metal center possessing a distorted-octahedral type of coordination, where the bpea ligand is coordinated in a meridional fashion in 2a and in a facial fashion in 2b and 3. The isomer 2a is the kinetically favored and thus can be thermally converted into 2b, that is the thermodynamically favored one. A thorough kinetic analysis strongly points toward a dissociative mechanism, where in the first step a chloro ligand is removed from the metal coordination sphere, followed by a geometric rearrangement before the chloro ligand coordinates again, generating the final complex. DFT calculations agree with the experimental data for the proposed mechanism and allow us to further characterize the mechanism of the 2a --> 2b rearrangement by obtaining the intermediates and transition state.

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Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Chemistry of Ru(II) Complexes Containing Cl and DMSO Ligands

et al. 2007

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The Chemistry of Ruthenium Oxidation Complexes

Griffith

2009

Catalysis by Metal Complexes

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Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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This is one of the most important classes of oxidation effected by Ru complexes, particularly by RuO 4 , [RuO 4 ] − , [RuO 4 ] 2− and RuCl 2 (PPh 3 ) 3 , though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6.In this chapter the first of the two most important categories of oxidations catalysed by Ru complexes (the other being alkene and alkyne oxidations in Chapter 3) are considered. The approach in this and subsequent chapters differs from that of Chapter 1, concentrating here on the substrate rather than on the oxidant. The text is divided into the categories of alcohols and their oxidations. There are summaries in section 2.3.6 of systems of limited applicability which are mentioned only in Chapter 1, and in section 2.3.7 of large-scale (>1 g) oxidations.The first oxidations of alcohols by stoicheiometric RuO 4 /H 2 O were reported in 1958, of primary alcohols to aldehydes or carboxylic acids and secondary alcohols to ketones [1]. The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].

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Oxidation of secondary alcohols byN-methylmorpholine-N-oxide (NMO) catalyzed by Ru(II) halosulfoxide complexes. A kinetic study

Cited by 5 publications

References 17 publications

Mechanistic Insights into the Chemistry of Ru(II) Complexes Containing Cl and DMSO Ligands

Mechanistic Insights into the Chemistry of Ru(II) Complexes Containing Cl and DMSO Ligands

The Chemistry of Ruthenium Oxidation Complexes

Oxidation of Alcohols, Carbohydrates and Diols

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