Ruthenium(III)-catalysed oxidation of secondary alcohols by N-methylmorpholine N-oxide (NMO)

Vijayasri, K.; Rajaram, J.; Kuriacose, J. C.

doi:10.1016/0304-5102(87)80064-0

Cited by 27 publications

(13 citation statements)

References 23 publications

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“…These authors propose a hydrogen atom (radical) abstraction by an (oxoido)ruthenium(V) intermediate. [9] Our observation is more in line with benzyl alcohol oxidation by quinolinium chlorochromate (ρ = -1.2).…”

Section: Resultssupporting

confidence: 85%

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Mechanism of Hydride Abstraction by Cyclopentadienone‐Ligated Carbonylmetal Complexes (M = Ru, Fe)

et al. 2008

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Cyclopentadienone‐ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re‐oxidize the intermediate ruthenium hydride without catalyst re‐oxidation becoming rate‐limiting. Furthermore, C–H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of ρ = –0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand‐directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultssupporting

confidence: 85%

“…Shvo's catalyst (1) was purchased from Strem and used as received. Pentacarbonyliron(0) [Fe(CO) 5 ] and nonacarbonyldiiron(0) [Fe 2 (CO) 9 ] were purchased from Strem, manipulated under air-free conditions and protected from light. Benzoquinone was recrystallized from ethanol and used as a yellow crystal.…”

Section: Methodsmentioning

confidence: 99%

Mechanism of Hydride Abstraction by Cyclopentadienone‐Ligated Carbonylmetal Complexes (M = Ru, Fe)

et al. 2008

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“…This was further supported by spectral changes that occur by addition of NMO to a dichloromethane solution of the ruthenium(II) complexes. The appearance of a peak at 390 nm is attributed to the formation of Ru IV =O species which is in conformity with other oxo ruthenium complexes [26,[35][36][37]. The proposed mechanism in the presence of molecular oxygen includes the oxidation of alcohol by a Ru n?…”

Section: Oxidation Of Alcoholsmentioning

confidence: 74%

Synthesis, spectroscopic, redox, catalytic and antimicrobial properties of some ruthenium(II) Schiff base complexes

Thilagavathi¹,

Manimaran

Priya

et al. 2009

Transition Met Chem

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A new series of mixed ligand semicarbazone or thiosemicarbazone complexes of Ru(II) having the general formula [RuCO(EPh 3 )(B)L] (where E = P or As; B = PPh 3 , AsPh 3 or Pyridine; L = dibasic tridentate ligand derived by the condensation of ethylacetoacetate/methylacetoacetate and thiosemicarbazide/semicarbazide) have been synthesized and characterized by physico-chemical, spectroscopic and electrochemical studies. A comparative study on the catalysis of oxidation of benzyl alcohol, cyclohexanol, cinnamyl alcohol, n-butanol, n-propanol and iso-butyl alcohol has been done with N-methylmorpholine-N-oxide and molecular oxygen as co-oxidants. Catalytic activity studies of the complexes in coupling reactions have been carried out. The antibacterial properties of the complexes have also been examined.

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“…Alcohol oxidation with 1 has isotope effects on both C-H (k H /k D = 2.6) and O-H(k H /k D = 1.8), which indicates that both of these hydrogen atoms are transferred in (or possibly before) the rate-determining transition state ( Figure 1A) [27]. Further, 1-catalyzed oxidation of 1-phenylethanol has a Hammett ρ value of −0.9, which is larger than expected for a transition state involving β-hydride elimination (ρ = −0.43) [29] or free-radical hydrogen atom transfer (ρ = −0.3) [30].…”

Section: Design Of a Dual Site Ruthenium Boron Catalystmentioning

confidence: 88%

Alcohol Dehydrogenation with a Dual Site Ruthenium, Boron Catalyst Occurs at Ruthenium

et al. 2012

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Ruthenium(III)-catalysed oxidation of secondary alcohols by N-methylmorpholine N-oxide (NMO)

Cited by 27 publications

References 23 publications

Mechanism of Hydride Abstraction by Cyclopentadienone‐Ligated Carbonylmetal Complexes (M = Ru, Fe)

Mechanism of Hydride Abstraction by Cyclopentadienone‐Ligated Carbonylmetal Complexes (M = Ru, Fe)

Synthesis, spectroscopic, redox, catalytic and antimicrobial properties of some ruthenium(II) Schiff base complexes

Alcohol Dehydrogenation with a Dual Site Ruthenium, Boron Catalyst Occurs at Ruthenium

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