Homogeneous catalysis of methyl formate production from carbon monoxide and methanol in the presence of metal carbonyl catalysts

Darensbourg, Donald J.; Gray, Robert L.; Ovalles, César; Pala, Magdalena

doi:10.1016/0304-5102(85)87011-5

Cited by 27 publications

(14 citation statements)

References 11 publications

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“…However, in THF solution, the chelated complexes [Et 4 N][W(CO) 4 (m-TU)], where the thiouracilate is bonded via the sulfur atom and the N-atom of the ring, were obtained. The results of the kinetics of COsubstitution in [(n-Bu) 4 N][M(CO) 5 SR] by P(OPr-i) 3 are also reported. [15] As an extension to our effort in the area of the reactivity of anionic metal carbonyls, especially those containing an M-S bond, this paper describes the synthesis of heterocyclic-thiolate complexes, [(n-Bu) 4 N][M-(CO) 5 SR], and their reactivity toward M'(CO) 5 THF in an attempt to obtain homo-and heterobimetallic complexes.…”

Section: Introductionmentioning

confidence: 90%

“…The most interesting feature of the reactions of these anionic complexes is their ability to undergo facile CO dissociation, to initially afford coordinatively unsaturated intermediates, followed by other fast steps. Thus, these anionic ligands were classified as cis-CO labilizing via an intramolecular ligand-assisted dissociation of CO. [1 -14] The labilizing nature of these ligands was explained in terms of ground state destabilization through distal 'hard' base-assisted cis-CO displacement and transition state stabilization via formation of a chelated [M(CO) 4 X] À intermediate. For example, acetate, [1,2] formate, [3,4] carboxylate, [5 -7] phenoxide, [8] glycinate, [9] uracilate [10] and thiobenzoate [11] complexes undergo faster CO-dissociation compared to the hexacarbonyl parent or to those containing neutral phosphine or phosphite ligands.…”

Section: Introductionmentioning

confidence: 99%

“…[15] These complexes were prepared from the reaction of M(CO) 5 -(MeOH) and the corresponding thiouracilate anion, where TU is bonded to tungsten via the exocyclic sulfur atom. [15] As an extension to our effort in the area of the reactivity of anionic metal carbonyls, especially those containing an M-S bond, this paper describes the synthesis of heterocyclic-thiolate complexes, [(n-Bu) 4 N][M-(CO) 5 SR], and their reactivity toward M'(CO) 5 THF in an attempt to obtain homo-and heterobimetallic complexes. The kinetics of CO dissociation in [W(CO) 5 (TU)] À supported a bond-breaking and a bondmaking type mechanism, i.e., M-CO bond-breaking and M -N bond-making occur concertedly.…”

Section: Introductionmentioning

confidence: 99%

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Novel Anionic Heterocyclic Thiolate Complexes of Group VIB Metal Carbonyls: Synthesis and Reactivity

Asali

El‐khateeb

Battaineh

2003

LSRT

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The syntheses and characterization of novel Group VIB metal carbonyl complexes containing heterocyclic thiolate ligands is described. The reactions of the photogenerated intermediate, M(CO) 5 THF (M = W, Mo, Cr), with the thiolate anions RS À in [(n-Bu) 4 N][SR] [SR À = 2mercaptobenzimidazolyl (a), 2-mercaptobenzothiazolyl (b), 2-mercaptobenzoxazolyl (c)], afforded exclusively [(n-Bu) 4 N][M(CO) 5 SR] in fairly good yields. Homo-and heterobimetallic complexes of the type [(n-Bu) 4 N][M(CO) 5 (m-SR)M'(CO) 5 ] (M, M' = W, Mo, Cr), in which both the exocyclic S-atom and the endocyclic N-atom are involved in coordination to two metal centers, have been prepared by the reaction of [(n-Bu) 4 N][M(CO) 5 SR] with M'(CO) 5 ÁTHF at ambient temperatures. The methods of preparation and characterization of these complexes are described. CO-substitution reactions in [(n-Bu) 4 N][W(CO) 5 SR] [SR À = (b) and (c)] with tri(iso-propyl)phosphite (L) afforded the complexes [(n-Bu) 4 N][cis-W(CO) 4 (SR){P(OPr-i) 3 }] as the sole reaction product.The kinetics of CO dissociation from the pentacarbonyl anions under pseudo-first-order conditions confirm that these reactions are firstorder in substrate and independent of the entering group (L) concentration. The facile CO dissociation in these complexes is another example of neighboring-group participation in assisting cis-CO loss in octahedral metal carbonyls. From the kinetics data, the anionic ligands (b) and (c) are classified as cis-CO labilizing groups. Rate constants and activation parameters for the CO-substitution reactions in these complexes are reported.

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Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Novel Anionic Heterocyclic Thiolate Complexes of Group VIB Metal Carbonyls: Synthesis and Reactivity

Asali

El‐khateeb

Battaineh

2003

LSRT

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“…0 ]~ ( Figure 6) (8,9). A catalytic scheme has been proposed for this reaction whereby the catalyst is heterolytically cleaved under CO pressure, yielding HW(C0) 5 " and W(C0) 6 (Scheme II).…”

Section: Methods For Acquiring Ir Spectral Data 233mentioning

confidence: 99%

New Methods for Acquiring IR Spectral Data in Organometallic Chemistry and Catalysis

Darensbourg

Gibson

1987

ACS Symposium Series

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The advent of new infrared sampling accessories has allowed in situ study of organometallic systems under conditions that were previously not readily accessible. The techniques of Cylindrical Internal Reflectance (CIR) and Diffuse Reflectance spectroscopies are described herein. The CIR phenomenon was employed in three different apparatus. Two different high pressure CIR cells were used to study reactions homogeneously catalyzed by [μ-HW 2 (CO)10]-. Low temperature reactions of Mo and W complexes were studied using an ambient pressure CIR cell. The diffuse reflectance technique was employed to study powdered samples of Ru carbonyl complexes supported on A1 2 O 3 .It would be a vast understatement to assert that infrared spectro scopy has played a major role in the characterization of organo metallic derivatives, in particular metal carbonyls (1,2). Hence, a discussion of the role of infrared spectroscopy in organometallic chemistry and catalysis in our introductory comments will be avoided. Nevertheless, it is unquestionably true that the enhanced signal/noise available via FTIR has dramatically changed IR spec troscopy. As the technology has changed, the accessories for sampling have changed (3). These in turn have resulted in a significant impact on the type and quality of experiments that can be readily performed.We wish to describe in this chapter some of the new and innov ative infrared accessories commercially available to the exper imental chemist. All of the infrared items described herein were obtained from Spectra Tech, Inc. (652 Glenbrook Road, P. 0. Box 2190-G, Stanford, CT 06906, Ph. (800)243-9186).The conditions for which we have demonstrated the use of these devices involving in situ infrared spectroscopy include the following:• High pressure and high temperature solution phase reactions carried out in both batch-mode or flow-through reactors.

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“…It is well known that alkali alkoxides are efficient catalysts for the former reaction [16,17] and that copperbased compounds such as copper chromite [18,19], Raney copper and silica-supported copper [20,21] show excellent catalytic activities for the latter. Thus, upon employing catalytic systems composed of both materials, the above two reactions proceed concurrently in a single reactor under the mild conditions of 373-453 K and 5.0-6.5 MPa to yield methanol from syngas, and gave high methanol synthesis rates and high one-pass CO conversions.…”

Section: B Xumentioning

confidence: 99%

A New Method of Low Temperature Methanol Synthesis

Yang

Meng

et al. 2009

Catal Surv Asia

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Low temperature methanol synthesis is a promising technique for the practical methanol industry. New developments of a new kind of low temperature methanol synthesis were reviewed, including the effects of feed gas, reaction solvent, supercritical media and catalyst modification. The reaction mechanism and kinetics were also summarized primarily. Carbon dioxide played an important role in this new kind of low temperature methanol synthesis. It reacted with hydrogen adsorbed on catalyst surface to form HCOOM, an important reaction intermediate. Alcohol solvent in the low temperature methanol synthesis performed not only a media, but also a homogeneous catalyst. The reaction of the adsorbed formate species with alcohol on Cu/ZnO catalyst surface proceeded according to the Rideal mechanism rather than Langmuir-Hinshelwood mechanism to form alkyl formate. The formation of alkyl formate from alcohol solvent and hydrogenation of such an alkyl formate were the key steps in low temperature methanol synthesis reaction. These results provided new insights into low temperature methanol synthesis.

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Homogeneous catalysis of methyl formate production from carbon monoxide and methanol in the presence of metal carbonyl catalysts

Cited by 27 publications

References 11 publications

Novel Anionic Heterocyclic Thiolate Complexes of Group VIB Metal Carbonyls: Synthesis and Reactivity

Novel Anionic Heterocyclic Thiolate Complexes of Group VIB Metal Carbonyls: Synthesis and Reactivity

New Methods for Acquiring IR Spectral Data in Organometallic Chemistry and Catalysis

A New Method of Low Temperature Methanol Synthesis

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