Carbon–hydrogen cleavage versus ring opening in the oxidative addition reactions of furan, thiophene, selenophene and tellurophene with [Os3(CO)10(MeCN)2]

Arce, Alejandro J.; Deeming, Antony J.; Sanctis, Ysaura De; Machado, Rubén; Manzur, Jorge; Rivas, Carlos

doi:10.1039/c39900001568

Cited by 63 publications

(19 citation statements)

References 9 publications

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“…[13][14][15] Similar results have been observed for 2-methylthiophene, 2,2Ј-bithiophene and 2,2Ј:5Ј,2ЈЈ-terthiophene. [16] The first room-temperature C-S bond cleavage of a (benzo)thiophene coordinated to a metallic cluster was reported by Arce et al [17] In chloroform at room temperature the cluster [Os 3 (µ-H)(CO) 10 (µ-C 8 H 5 S)], which contains a µ-η 2 -benzothienyl ligand, undergoes C(vinyl)-S bond cleavage to yield the cluster [Os 3 (CO) 10 (µ-C 8 H 6 S)], which contains an open benzothiophene ligand coordinated to an open Os 3 unit through a µ-S atom and a µ-η 2 -vinyl group (Scheme 2).…”

Section: P{supporting

confidence: 88%

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: P{supporting

confidence: 88%

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

et al. 2006

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“…The reaction of [Ru 3 (CO) 12 ] with thiophene proceeds similarly via C-S cleavage giving [Ru 2 (l-C 4 H 4 )(CO) 6 ] and [Ru 4 (l 3 -S)(l-C 4 H 4 )(CO) 11 ] [5]. It has been demonstrated that C-H bond activation predominates over C-S cleavage when thiophene reacts with [Os 3 (CO) 12 ] and [Os 3 (CO) 10 benzothiophene when coordinated to a triosmium cluster [Os 3 (l 3 -S)(l-C 8 H 5 S)(CO ) 10 ] has been reported to give [Os 3 (l-C 8 H 6 S)( CO) 10 ] which contains an open benzothiophene ligand coordinated to an open Os 3 unit through a l-S and l-g 2 -vinyl group [7,8].…”

Section: Introductionmentioning

confidence: 99%

Two modes of C–H bond activation of tris(2-thienyl)phosphine in trinuclear osmium carbonyl clusters

Mottalib¹,

Kabir²,

Tocher³

et al. 2007

Journal of Organometallic Chemistry

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“…42 Since the C 4 H 3 isomers are extremely reactive, isolation is restricted to a low temperature matrix ͑n-C 4 H 3 ͒ or trapping as an 1,3-3 -dimetalated cyclic species (M 1) as well as 1,3,3-4 -trimetalated chain isomer (M 2). [43][44] In this paper, we investigate the detailed chemical dynamics of the atom-neutral reaction of C͑ 3 P j ͒ with methylacetylene, CH 3 CCH(X 1 A 1 ) under single collision conditions at collision energies of 20.4 and 33.2 kJmol Ϫ1 as provided in crossed molecular beam experiments. The insights into the reaction dynamics disclose precise information on the hitherto unexplored triplet C 4 H 4 and doublet C 4 H 3 potential energy surface ͑PES͒ under well-defined collision energies, and potential exit channel͑s͒ to C 4 H 3 isomers.…”

Section: Introductionmentioning

confidence: 99%

Crossed-beam reaction of carbon atoms with hydrocarbon molecules. II. Chemical dynamics of n-C4H3 formation from reaction of C(3P j) with methylacetylene, CH3CCH (X1A1)

Kaiser

Stranges

Lee

et al. 1996

The Journal of Chemical Physics

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The reaction between ground-state carbon atoms, C(3Pj), and methylacetylene, CH3CCH (X1A1), was studied at average collision energies of 20.4 and 33.2 kJ mol−1 using the crossed molecular beams technique. Product angular distributions and time-of-flight spectra of C4H3 at m/e=51 were recorded. Forward-convolution fitting of the data yields weakly polarized center-of-mass angular flux distributions isotropic at lower, but forward scattered with respect to the carbon beam at a higher collision energy. The translational energy flux distributions peak at 30–60 kJ mol−1 and show an average fractional translational energy release of 22%–30%. The maximum energy release as well as the angular distributions are consistent with the formation of the n-C4H3 radical in its electronic ground state. Reaction dynamics inferred from these distributions indicate that the carbon atom attacks the π-orbitals of the methylacetylene molecule via a loose, reactant like transition state located at the centrifugal barrier. The initially formed triplet 1-methylpropendiylidene complex rotates in a plane almost perpendicular to the total angular momentum vector around the B\C-axes and undergoes [2,3]-hydrogen migration to triplet 1-methylpropargylene. Within 1–2 ps, the complex decomposes via C–H bond cleavage to n-C4H3 and atomic hydrogen. The exit transition state is found to be tight and located at least 30–60 kJ mol−1 above the products. The explicit identification of the n-C4H3 radical under single collision conditions represents a further example of a carbon–hydrogen exchange in reactions of ground state carbon atoms with unsaturated hydrocarbons. This channel opens a versatile pathway to synthesize extremely reactive hydrocarbon radicals relevant to combustion processes as well as interstellar chemistry.

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Carbon–hydrogen cleavage versus ring opening in the oxidative addition reactions of furan, thiophene, selenophene and tellurophene with [Os₃(CO)₁₀(MeCN)₂]

Cited by 63 publications

References 9 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

Two modes of C–H bond activation of tris(2-thienyl)phosphine in trinuclear osmium carbonyl clusters

Crossed-beam reaction of carbon atoms with hydrocarbon molecules. II. Chemical dynamics of n-C4H3 formation from reaction of C(3P j) with methylacetylene, CH3CCH (X1A1)

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