Specific oxidation of bis(chlorodicarbonylrhodium) by oxygen via the coordination of in situ generated hydrogen peroxide. Implications for the rhodium(III)/copper(III)-catalyzed oxygen oxidation of 1-alkenes to 2-ketones

Nyberg, Eric D.; Pribich, David C.; Drago, Russell S.

doi:10.1021/ja00349a028

Cited by 28 publications

(5 citation statements)

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“…However, if CDCl 3 was used instead of C 6 D 6 , the transformation occurred in 5 days, and it was possible to observe the formation of 2,4-pentadienal, as well as the corresponding intermediate 9 (Scheme ). This sort of transformation, assisted by chlorinated solvents, has been observed in terminal alkene oxidations based on dichlororuthenium(IV)-porphyrin catalysts in chlorinated solvents, such as CHCl 3 or CH 2 Cl 2 , which produced aldehydes in quantitative yields …”

Section: Resultsmentioning

confidence: 77%

“…These reactions could occur by activation of molecular oxygen from the air, as it has been observed for the oxidation of alkenes in the presence of oxygen . However, if CDCl 3 was used instead of C 6 D 6 , the transformation occurred in 5 days, and it was possible to observe the formation of 2,4-pentadienal, as well as the corresponding intermediate 9 (Scheme ).…”

Section: Resultsmentioning

confidence: 94%

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Comparative Study of the Reactivity of (CpRuCl)₄and (CpRuCl₂)₂with Silylated Dienyl Ligands

Sánchez-Castro

Paz-Sandoval

2008

Organometallics

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Reaction of the well-known precursors [Cp*RuCl] 4 (1) and [Cp*RuCl 2 ] 2 (2) with the silyl-diene compound CH 2 dCHCHdCHCH 2 SiMe 3 (3), in THF, results in the selective formation of [Cp*Ru(η 4 -CH 2 CHCHCHCH 2 SiMe 3 )Cl] (4) from the diamagnetic tetramer 1, while the reaction of dimer 2 leads to nonselective reactions with the formation of 4, [Cp*Ru(η 3 -CH 2 CHCHCHCH 2 )Cl 2 ] (5), and [Cp*Ru(η 3 -CH 2 CHCHCHCHSiMe 3 )Cl 2 ] (6). Reaction of 2 with 3, in ethanolic solution at room temperature, provided a preparative route to the corresponding diene 4 and the allyl ruthenium(IV) complex 5. Compound 4, in the presence of chloroform, affords 6, and recrystallization of 5 with CH 2 Cl 2 /hexane affords [Cp*Ru(η 3 -CH 2 CHCHEt)Cl 2 ] (7), but contrastingly, the manipulation of compound 5 in plates of silica gel affords [Cp*Ru(η 4 -CH 2 CHCHCHCH 2 OH)Cl] (8). A CDCl 3 or C 6 D 6 solution of 8 in the presence of traces of oxygen affords Cp*Ru(η 4 -CH 2 CHCHCHCHO)Cl ( 9), which slowly decomposes to liberate 2,4-pentadienal in the reaction media, along with unknown Cp*Ru species. A comparative study is established between the chemical reactivity of 1 and 2 toward the trimethylsilylpentadiene and the corresponding analogous trimethylsilyl-substituted dienyloxy ligands. Some representative crystalline structures of compounds 4, 6, and 8 were determined by X-ray crystallography.⊥ Dedicated to Professor Heinrich Nöth, friend and colleague, on the occasion of his 80th birthday and in recognition of his seminal contributions in chemistry.

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Section: Resultsmentioning

confidence: 77%

Section: Resultsmentioning

confidence: 94%

Comparative Study of the Reactivity of (CpRuCl)₄and (CpRuCl₂)₂with Silylated Dienyl Ligands

Sánchez-Castro

Paz-Sandoval

2008

Organometallics

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“…It has been reported that certain Rh compounds, especially in the presence of alcohols and Cu compounds, can directly activate molecular oxygen to react with ot-olefins to produce methyl ketones with selectivities as high as 98% and little isomerization. A review of the literature [45][46][47][48][49][50][51][52][53] yields the following list of desirable components:…”

Section: Calcining One Of the Catalysts At 250°c Increased The Total mentioning

confidence: 99%

“…The first of these is playing a part in generating an active cationic Rh species [45, 46b, 48]. The second role proposed for copper is as a catalyst for the reduction of 0 2 to H20 2 [47,48]. H20 2 may react with Rh to form the hydroperoxo Rh species which are thought to be intermediates in the olefin oxidation reaction [48,50,52].…”

Section: Calcining One Of the Catalysts At 250°c Increased The Total mentioning

confidence: 99%

“…However, there is at least one report on Rh catalysts without Cu additives that indicates that oxygen concentration does affect the reaction rate [46a]. Furthermore, another report indicates that at least one step in the conversion of the Rh(I) complex [Rh(CO)2CI]2 to an active Rh(III) catalyst shows a first order dependence on oxygen concentration in the absence of Cu [47]. When this same Rh(I) complex is used as a catalyst without added Cu, an induction period is observed whose length shows an inverse first order dependence on the oxygen concentration.…”

Section: Calcining One Of the Catalysts At 250°c Increased The Total mentioning

confidence: 99%

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Hydrous metal oxide catalysts for oxidation of hydrocarbons

Miller¹,

Dosch²,

McLaughlin³

1993

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This report describes work performed at Sandia under a CRADA with Shell Development of Houston, Texas aimed at developing hydrous metal oxide (HMO) catalysts for oxidation of hydrocarbons. Autoxidation as well as selective oxidation of 1-octene was studied in the presence of HMO catalysts based on known oxidation catalysts. The desired reactions were the conversion of olefin to epoxides, alcohols, and ketones. HMOs seem to inhibit autoxidation reactions, perhaps by reacting with peroxides or radicals. Attempts to use HMOs and metal loaded HMOs as epoxidation catalysts were unsuccessful, although their utility for this reaction was not entirely ruled out. Likewise, alcohol formation from olefins in the presence of HMO catalysts was not achieved. However, this work led to the discovery that acidified HM0s can lead to carbocation reactions of hydrocarbons such as cracking. An HMO catalyst containing Rh and Cu that promotes the reaction of ct-olefins with oxygen to form methyl ketones was identified. Although the activity of the catalyst is relatively low and isomerization reactions of the olefin simultaneously occur, results indicate that these problems may be addressed by eliminating mass transfer limitations. Other suggestions for improving the catalyst are also made.

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ChemInform Abstract: SPECIFIC OXIDATION OF BIS(CHLORODICARBONYLRHODIUM) BY OXYGEN VIA THE COORDINATION OF IN SITU GENERATED HYDROGEN PEROXIDE. IMPLICATIONS FOR THE RHODIUM(III)/COPPER(III)‐CATALYZED OXYGEN OXIDATION OF 1‐ALKENES TO 2‐KETONES

Nyberg¹,

Pribich²,

Drago³

1983

Chemischer Informationsdienst

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Specific oxidation of bis(chlorodicarbonylrhodium) by oxygen via the coordination of in situ generated hydrogen peroxide. Implications for the rhodium(III)/copper(III)-catalyzed oxygen oxidation of 1-alkenes to 2-ketones

Cited by 28 publications

References 5 publications

Comparative Study of the Reactivity of (CpRuCl)₄and (CpRuCl₂)₂with Silylated Dienyl Ligands

Comparative Study of the Reactivity of (CpRuCl)₄and (CpRuCl₂)₂with Silylated Dienyl Ligands

Hydrous metal oxide catalysts for oxidation of hydrocarbons

ChemInform Abstract: SPECIFIC OXIDATION OF BIS(CHLORODICARBONYLRHODIUM) BY OXYGEN VIA THE COORDINATION OF IN SITU GENERATED HYDROGEN PEROXIDE. IMPLICATIONS FOR THE RHODIUM(III)/COPPER(III)‐CATALYZED OXYGEN OXIDATION OF 1‐ALKENES TO 2‐KETONES

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Specific oxidation of bis(chlorodicarbonylrhodium) by oxygen via the coordination of in situ generated hydrogen peroxide. Implications for the rhodium(III)/copper(III)-catalyzed oxygen oxidation of 1-alkenes to 2-ketones

Cited by 28 publications

References 5 publications

Comparative Study of the Reactivity of (Cp*RuCl)4and (Cp*RuCl2)2with Silylated Dienyl Ligands

Comparative Study of the Reactivity of (Cp*RuCl)4and (Cp*RuCl2)2with Silylated Dienyl Ligands

Hydrous metal oxide catalysts for oxidation of hydrocarbons

ChemInform Abstract: SPECIFIC OXIDATION OF BIS(CHLORODICARBONYLRHODIUM) BY OXYGEN VIA THE COORDINATION OF IN SITU GENERATED HYDROGEN PEROXIDE. IMPLICATIONS FOR THE RHODIUM(III)/COPPER(III)‐CATALYZED OXYGEN OXIDATION OF 1‐ALKENES TO 2‐KETONES

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Comparative Study of the Reactivity of (CpRuCl)₄and (CpRuCl₂)₂with Silylated Dienyl Ligands

Comparative Study of the Reactivity of (CpRuCl)₄and (CpRuCl₂)₂with Silylated Dienyl Ligands