Oxidation of [CpMo(CO)3R] olefin epoxidation precatalysts with tert-butylhydroperoxide

Grover, Nidhi; Drees, Markus; Kühn, Fritz E.

doi:10.1016/j.jcat.2015.05.019

Cited by 13 publications

(17 citation statements)

References 81 publications

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“…Studies concerning mechanistic pathways and decomposition reactions, performed in the presence of low olefin concentrations, showed that several side reactions occur that had not been considered in the original mechanistic proposals. As expected, at least for some Mo‐based catalysts, the catalytic reactions seem to be more sophisticated than originally assumed …”

Section: Molybdenum‐containing Compounds In Oxidation Catalysissupporting

confidence: 68%

Molecular Epoxidation Reactions Catalyzed by Rhenium, Molybdenum, and Iron Complexes

Kück

Reich

Kühn

2016

The Chemical Record

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The reactions of a diborene with elemental selenium or tellurium are shown to afford a diboraselenirane or diboratellurirane, respectively. These reactions are reminiscent of the sequestration of sub-valent oxygen and nitrogen in the formation of oxiranes and aziridines; however, such reactivity is not known between alkenes and the heavy chalcogens. While carbon is too electronegative to affect the reduction of elements of lower relative electronegativity, the highly reducing nature of the B=B double bond enables reactions with Se 0 and Te 0. The capacity of multiple bonds between boron to donate electron density is highlighted in reactions where diborynes behave as nucleophiles, attacking one of the two Te atoms of diaryltellurides, forming salts consisting of diboratellurenium cations and aryltelluride anions.

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Section: Molybdenum‐containing Compounds In Oxidation Catalysissupporting

confidence: 68%

Molecular Epoxidation Reactions Catalyzed by Rhenium, Molybdenum, and Iron Complexes

Kück

Reich

Kühn

2016

The Chemical Record

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“…Induction periods have often been observed for cyclopentadienyl molybdenum(II) tricarbonyl complexes [ η 5 ‐CpMo(CO) 3 R] (R = alkyl, halide) when used as pre‐catalysts for the epoxidation of olefins with tert ‐butylhydroperoxide as oxidant . These complexes are known to undergo oxidative decarbonylation to give catalytically active dioxo [ η 5 ‐CpMoO 2 R] and oxoperoxo [ η 5 ‐CpMo(O)(O 2 )R] complexes . In the case of complex 1 with H 2 O 2 , oxidative decarbonylation of the complex is indicated by its solubilization together with a change in color to yellow after the first minute of the reaction (Figure ), which is the usual color of oxoperoxomolybdenum(VI) complexes.…”

Section: Resultsmentioning

confidence: 99%

Desulfurization of model and real fuels by extraction and oxidation processes using an indenylmolybdenum tricarbonyl pre‐catalyst

Julião

Gomes

Pillinger

et al. 2020

Applied Organom Chemis

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Regulations on the permissible levels of sulfur in transportation fuels are becoming ever more strict, with a global shift towards “zero sulfur” fuels, and the revamp of existing hydrodesulfurization (HDS) facilities to meet these lower caps is cost‐prohibitive. Metal‐catalyzed sulfoxidation chemistry is viewed as an economically viable desulfurization strategy that could complement conventional HDS technology. In the present work, the complex [η5‐IndMo(CO)3Me] (1) (Ind = indenyl) was employed in the catalytic oxidative desulfurization (CODS) of model and real liquid fuels, using aqueous hydrogen peroxide (H2O2) as oxidant. After optimization of the CODS reaction parameters (diesel/H2O2 ratio, catalyst amount, temperature), a high‐sulfur (2000 ppm) model diesel containing benzothiophene, dibenzothiophene, 4‐methyldibenzothiophene and 4,6‐dimethyldibenzothiophene could be completely desulfurized within 2 hr under solvent‐free conditions or in the presence of the ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM]PF6) as extraction solvent. The catalyst formed under solvent‐free conditions could be recycled without a significant decrease in desulfurization activity. The high performance of the CODS system was verified in the sulfur removal from a commercial untreated diesel fuel with a sulfur content of 2300 ppm, and a jet fuel with a sulfur content of 1100 ppm. Solvent‐free CODS in combination with initial/final extraction gave desulfurization efficiencies of 70% for the diesel fuel and 55% for the jet fuel. CODS with [BMIM]PF6 in combination with initial/final extraction led to a sulfur removal of 95.9% for the diesel fuel, which is one of the best results yet reported for ODS of commercial diesels.

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“…The solvent of choice for mechanistic purposes is CHCl 3 as it was recently found that decarbonylation is quite slow in it and is therefore easier to follow and to distinguish from the catalytic epoxidation process. 20,27 Unfortunately, as the oxidized derivatives and the active species could not be isolated aat least at first glance somewhat clumsy pathway to unravel more mechanistic details is necessary. Comparison of the behaviour of 1-3 shows an increasing induction period (which occurs under applied conditions only with a low excess of TBHP) with an increasing distance from the metal centre to the CF 3 moiety (Fig.…”

Section: Influence Of the Position Of A Cf 3 Group On Catalysismentioning

confidence: 99%

Kinetic studies of fluorinated aryl molybdenum(ii) tricarbonyl precursors in epoxidation catalysis

Reich

Kaposi

Pöthig

et al. 2016

Catal. Sci. Technol.

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Oxidation of [CpMo(CO)3R] olefin epoxidation precatalysts with tert-butylhydroperoxide

Cited by 13 publications

References 81 publications

Molecular Epoxidation Reactions Catalyzed by Rhenium, Molybdenum, and Iron Complexes

Molecular Epoxidation Reactions Catalyzed by Rhenium, Molybdenum, and Iron Complexes

Desulfurization of model and real fuels by extraction and oxidation processes using an indenylmolybdenum tricarbonyl pre‐catalyst

Kinetic studies of fluorinated aryl molybdenum(ii) tricarbonyl precursors in epoxidation catalysis

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