Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Ogilvy, Ann E.; Draganjac, M.; Rauchfuss, Thomas B.; Wilson, Scott R.

doi:10.1021/om00095a024

Cited by 125 publications

(83 citation statements)

References 6 publications

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“…However, the low-temperature 31 P{ 1 H} NMR spectrum of 2 indicates the presence of more than one isomer. The two most reasonable isomers are the cis-trans and transtrans isomers (cis or trans with respect to the Os-Os vector) shown in Figure 1, which have previously been detected for related [Os 3 (CO) 10 (phosphane) 2 ] clusters. [25,26] The 31 P{ 1 H} NMR spectrum at -60°C (Figure 1) reveals that the predominant form is the cis-trans isomer with non-equivalent phosphorus nuclei, represented by two singlets at δ = -18.12 and -21.97 ppm.…”

Section: Thermal Treatment Of [Os 3 (Co) 12 ] With Ph 2 P(c 4 H 3 S)supporting

confidence: 57%

“…In addition to 2, the solid-state structures of 3, 5 and One of the very first reports of the interaction of thiophene with organometallic compounds described the desulfurisation of the heterocycle by a metal cluster, [Fe 3 (CO) 12 ]. [8,9] Rauchfuss and co-workers [10] demonstrated shortly after, that thiaferroles are easily converted into the corresponding ferroles on heating and thereby established that insertion of an iron atom into a C-S bond clearly activates the heterocycle towards desulfurisation [Scheme 1(a)]. Similarly, the reaction of [Ru 3 (CO) 12 ] with thiophene proceeds through C-S bond cleavage, producing the sulfur-free ferrole-type compound [Ru 2 (µ-C 4 H 4 )(CO) 6 ] and the tetranuclear cluster [Ru 4 (µ 3 -S)(µ-C 4 H 4 )(CO) 11 ]; [11] this is the first reported example of desulfurisation of a thiophene in which both the extruded sulfur and the hydrocarbon residue remain coordinated within the same complex [Scheme 1(b)].…”

Section: P{mentioning

confidence: 99%

“…Similarly, the reaction of [Ru 3 (CO) 12 ] with thiophene proceeds through C-S bond cleavage, producing the sulfur-free ferrole-type compound [Ru 2 (µ-C 4 H 4 )(CO) 6 ] and the tetranuclear cluster [Ru 4 (µ 3 -S)(µ-C 4 H 4 )(CO) 11 ]; [11] this is the first reported example of desulfurisation of a thiophene in which both the extruded sulfur and the hydrocarbon residue remain coordinated within the same complex [Scheme 1(b)]. More recently, Angelici and co-workers [12] have demonstrated [Re 2 (CO) 10 ]-promoted C-S bond cleavage in benzothiophenes.…”

Section: P{mentioning

confidence: 99%

“…[18][19][20] Treatment of diphenyl(2-thienyl)phosphane with [Ru 3 (CO) 12 ] has led to the incorporation of the thiophene ring into tri-and tetraruthenium clusters by cyclometallation and C-P bond cleavage of the ligand. [20] Here we report the reactions of [Os 3 10 ] with diphenyl(2-thienyl)phosphane, Ph 2 P(C 4 H 3 S), which have been undertaken in an effort to achieve C-P and C-S bond cleavage of the ligand.…”

Section: P{mentioning

confidence: 99%

“…Reaction of [H 2 Os 3 (CO) 10 ] with diphenyl(2-thienyl)phosphane at ambient temperature affords [HOs 3 (µ-H)(CO) 10 …”

mentioning

confidence: 99%

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Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

et al. 2006

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Thermal treatment of [Os3(CO)12] with diphenyl(2‐thienyl)phosphane, Ph2P(C4H3S), results in the formation of [Os3(CO)12–x{Ph2P(C4H3S)}x] (x = 1–3, 1–3), but no C–H bond activation was observed. Reaction of [H2Os3(CO)10] with diphenyl(2‐thienyl)phosphane at ambient temperature affords [HOs3(μ‐H)(CO)10{Ph2P(C4H3S)}] (4), but when the samereaction is repeated at elevated temperatures, the cyclometallated species [(μ‐H)Os3(CO)9{μ3‐Ph2P(C4H2S)}] (5) and[(μ‐H)Os3(CO)8{μ3‐Ph2P(C4H2S)}{Ph2P(C4H3S)}] (6) are formed. In addition, two more products, tentatively assigned as [(μ‐H)Os3(CO)6{μ3‐Ph2P(C4H2S)}{μ‐Ph2P(C4H3S)}{Ph2P(C4H3S)}] (7) and [(μ‐H)Os3(CO)7{μ‐Ph2P(C4H2S)}{μ‐Ph2P(C4H3S)}{Ph2P(C4H3S)}] (8) are obtained. The dynamic behaviours of 2, 5 and 6 have been studied by variable‐temperature (VT) 1H and 31P{1H} NMR spectroscopy. The VT 31P{1H} NMR spectra of [Os3(CO)10{Ph2P(C4H3S)}2] (2) demonstrate that a mixture of two isomers, which are in rapid exchange at room temperature, is present and that the less common cis‐trans isomer, whose structure has been determined by X‐ray crystallography, is favoured for this cluster. The VT 1H NMR spectra of 5 indicate the presence of two isomers which are proposed to arise from an oscillation of the σ,η2‐vinyl group of the thienyl moiety between two metal atoms. A similar fluxional process is proposed to occur in 6 and the assignment of the room‐temperature structure(s) of this cluster was confirmed by 1H‐187Os 2D HMQC spectroscopy. In addition to 2, the solid‐state structures of 3, 5 and 6 have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Thermal Treatment Of [Os 3 (Co) 12 ] With Ph 2 P(c 4 H 3 S)supporting

confidence: 57%

Section: P{mentioning

confidence: 99%

Section: P{mentioning

confidence: 99%

Section: P{mentioning

confidence: 99%

“…Reaction of [H 2 Os 3 (CO) 10 ] with diphenyl(2-thienyl)phosphane at ambient temperature affords [HOs 3 (µ-H)(CO) 10 …”

mentioning

confidence: 99%

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Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

et al. 2006

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π-Conjugated Benzoperylenes: Sequential C–S Bond Cleavage and Charge Distribution Patterns of the Anions

Benshafrut

Rabinovitz²,

Hoffman

et al. 1999

Eur. J. Org. Chem.

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Chemical reduction of polyaromatic hydrocarbons yielded solutions of long‐lived polyanionic species. Reduction of a sulfur heterocycle afforded a stable sulfur‐containing dianion. Sulfur extrusion from this dianion proceeded upon further contact with the reducing metal. NMR and UV studies indicate a sulfur extrusion mechanism different than that previously observed in THF. Electron transfer to the already reduced hydrocarbon skeleton results in the stepwise cleavage of the two C–S bonds and the extrusion of a sulfur atom. Dimers of aromatic hydrocarbons such as pyrene and phenanthrene have been reduced as well. The interplay between coulombic repulsions and resonance energies is described.

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Hydrodesulfurization – Homogeneous

Sánchez‐Delgado

2002

Encyclopedia of Catalysis

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In spite of the large‐scale industrial applications of the hydrodesulfurization (HDS) process, and of the large number of studies of this reaction on heterogeneous catalysts, some aspects of the mechanisms involved are not yet fully understood. This article summarizes the most striking aspects of coordination and organometallic chemistry that are pertinent to the activation, hydrogenation, and desulfurization of thiophenes, in a systematic way, and inasmuch as possible in connection with the common knowledge and beliefs of the mechanisms of heterogeneous HDS catalysis. The binding of thiophenes to transition metals in molecular complexes, as well as the reactivity of such complexes in solution, is described in detail, with particular emphasis on reaction mechanisms. The examples presented are excellent molecular analogues of the species and reactions that are known or thought to intervene in heterogeneous catalysis, and thus this organometallic approach constitutes a good complement to surface and solid‐state chemistry studies and contributes to the understanding of this important reaction.

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Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Cited by 125 publications

References 6 publications

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

π-Conjugated Benzoperylenes: Sequential C–S Bond Cleavage and Charge Distribution Patterns of the Anions

Hydrodesulfurization – Homogeneous

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