One-step carboxylation reaction of saturated hydrocarbons with CO by Co(OAc)2 catalyst under mild conditions

Asadullah, Mohammad; Taniguchi, Yoshihiro; Kitamura, Tsugio; Fujiwara, Yoshiyuki

doi:10.1016/s0926-860x(99)00390-7

Cited by 21 publications

(7 citation statements)

References 52 publications

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“…It has been reported that cobalt,7g,11 copper,7a,9a,12 rare‐earth‐metal,13 manganese,14 and vanadium7d,7i,9a,15 salts as well as heteropolyanions15d,16 are capable of oxidizing methane in trifluoroacetic acid by radical pathways. Although some [11a,11b,11e,11f,14] of these systems have been shown to work with the oxidant dioxygen without the addition of a co‐reductant, the reported chemoselectivities are very modest as significant over‐oxidation occurs.…”

Section: Introductionmentioning

confidence: 99%

Cobalt‐Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen

et al. 2013

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Section: Introductionmentioning

confidence: 99%

Cobalt‐Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen

et al. 2013

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“…[17][18][19][20] Since the discovery in 1992 by Fujiwara's group of the direct conversion of methane into acetic acid catalyzed by CuSO 4 /Pd(OCOEt) 2 in trifluoroacetic acid (TFA) in the presence of K 2 S 2 O 8 , 20 several other catalysts and routes of methane carboxylation to acetic acid or its derivatives have been reported. 17,18,[21][22][23][24][25][26][27][28][29][30][31][32][33][34] However, most of these processes and catalytic systems still display a limited efficiency providing low or modest yields (relative to methane) and low turnover numbers (TONs), even when operating under harsh conditions and based on an expensive metal catalyst, and their mechanisms remain unknown. A recent achievement is the interesting oxidative condensation of CH 4 to CH 3 COOH (ca.…”

Section: Introductionmentioning

confidence: 99%

Direct and Remarkably Efficient Conversion of Methane into Acetic Acid Catalyzed by Amavadine and Related Vanadium Complexes. A Synthetic and a Theoretical DFT Mechanistic Study

Kirillova¹,

Kuznetsov²,

Reis³

et al. 2007

J. Am. Chem. Soc.

152

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Vanadium(IV or V) complexes with N,O- or O,O-ligands, i.e., [VO{N(CH2CH2O)3}], Ca[V(HIDPA)2] (synthetic amavadine), Ca[V(HIDA)2], or [Bu4N]2[V(HIDA)2] [HIDPA, HIDA = basic form of 2,2'-(hydroxyimino)dipropionic or -diacetic acid, respectively], [VO(CF3SO3)2], Ba[VO(nta)(H2O)]2 (nta = nitrilotriacetate), [VO(ada)(H2O)] (ada = N-2-acetamidoiminodiacetate), [VO(Hheida)(H2O)] (Hheida = 2-hydroxyethyliminodiacetate), [VO(bicine)] [bicine = basic form of N,N-bis(2-hydroxyethyl)glycine], and [VO(dipic)(OCH2CH3)] (dipic = pyridine-2,6-dicarboxylate), are catalyst precursors for the efficient single-pot conversion of methane into acetic acid, in trifluoroacetic acid (TFA) under moderate conditions, using peroxodisulfate as oxidant. Effects on the yields and TONs of various factors are reported. TFA acts as a carbonylating agent and CO is an inhibitor for some systems, although for others there is an optimum CO pressure. The most effective catalysts (as amavadine) bear triethanolaminate or (hydroxyimino)dicarboxylates and lead, in a single batch, to CH3COOH yields > 50% (based on CH4) or remarkably high TONs up to 5.6 x 103. The catalyst can remain active upon multiple recycling of its solution. Carboxylation proceeds via free radical mechanisms (CH3* can be trapped by CBrCl3), and theoretical calculations disclose a particularly favorable process involving the sequential formation of CH3*, CH3CO*, and CH3COO* which, upon H-abstraction (from TFA or CH4), yields acetic acid. The CH3COO* radical is formed by oxygenation of CH3CO* by a peroxo-V complex via a V{eta1-OOC(O)CH3} intermediate. Less favorable processes involve the oxidation of CH3CO* by the protonated (hydroperoxo) form of that peroxo-V complex or by peroxodisulfate. The calculations also indicate that (i) peroxodisulfate behaves as a source of sulfate radicals which are methane H-abstractors, as a peroxidative and oxidizing agent for vanadium, and as an oxidizing and coupling agent for CH3CO* and that (ii) TFA is involved in the formation of CH3COOH (by carbonylating CH3*, acting as an H-source to CH3COO*, and enhancing on protonation the oxidizing power of a peroxo-VV complex) and of CF3COOCH3 (minor product in the absence of CO).

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“…It is very worth noting that cobalt compounds have been known for a long time to be very active in the oxidation of C–H bonds. − Tang and Kochi already reported in 1973 that cobalt(III) reacts instantaneously at room temperature in HOFTA with alkanes like cyclohexane . It has been described that the aerobic oxidation of hydrocarbons by cobalt(III) compounds can involve the formation of peroxo complexes, whose decomposition yields oxygen-based radicals that initiate radical-based processes .…”

Section: Alkane Functionalization and Oxygen Activation By Cobalt Cat...mentioning

confidence: 99%

Alkane C–H Functionalization and Oxidation with Molecular Oxygen

Munz

Straßner

2015

Inorg. Chem.

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The application of environmentally benign, cheap, and economically viable oxidation procedures is a key challenge of homogeneous, oxidative alkane functionalization. The typically harsh reaction conditions and the propensity of dioxygen for radical reactivity call for extraordinary robust catalysts. Mainly three strategies have been applied. These are (1) the combination of a catalyst responsible for C-H activation with a cocatalyst responsible for dioxygen activation, (2) transition-metal catalysts, which react with both hydrocarbons and molecular oxygen, and (3) the introduction of very robust main-group element catalysts for C-H functionalization chemistry. Herein, these three approaches will be assessed and exemplified by the reactivity of chelated palladium (N-heterocyclic carbene) catalysts in combination with a vanadium cocatalyst, the methane functionalization by cobalt catalysts, and the reaction of group XVII compounds with alkanes.

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One-step carboxylation reaction of saturated hydrocarbons with CO by Co(OAc)2 catalyst under mild conditions

Cited by 21 publications

References 52 publications

Cobalt‐Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen

Cobalt‐Catalyzed Oxidation of Methane to Methyl Trifluoroacetate by Dioxygen

Direct and Remarkably Efficient Conversion of Methane into Acetic Acid Catalyzed by Amavadine and Related Vanadium Complexes. A Synthetic and a Theoretical DFT Mechanistic Study

Alkane C–H Functionalization and Oxidation with Molecular Oxygen

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