Thermal Fragmentation of Acyl Thiolato Complexes to Reactive Metal Sulfido Intermediates. Structure of Ru(.eta.6-SC3Me3COMe)(PPh3)2

Feng, Qian; Krautscheid, Harald; Rauchfuss, Thomas B.; Skaugset, Anton E.; Venturelli, Anne

doi:10.1021/om00001a043

Cited by 20 publications

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“…Recent examples of desulfurization of thiophenes by polynuclear complexes have been reported by Curtis,30 Angelici, 31 Rauchfuss, 32 Jones, 29 and Bianchini. 28 Among these, the overall degradation of T assisted by the cluster Cp′ 2 Mo 2 Co 2 S 3 (CO) 4 (Cp′ ) CH 3 C 5 H 4 ) is the model reaction that, in our opinion, best resembles the heterogeneous counterparts, particularly those classified as "Co/Mo/S" phase, 1a in terms of both structural motif and HDS activity (the hydrogen atoms necessary for the hydrogenolysis step are in fact externally added and not already incorporated into the organometallic precursor) (Scheme 9a).…”

Section: Desulfurization Of Thiophenic Substrates To Hydrocarbons Wit...mentioning

confidence: 99%

Hydrogenation, Hydrogenolysis, and Desulfurization of Thiophenes by Soluble Metal Complexes: Recent Achievements and Future Directions

1998

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Petroleum and natural gas contain various organosulfur compounds, and their removal by hydrodesulfurization (HDS) over heterogeneous catalysts (eq 1) produces hydrocarbons and H 2 S, 1 which may be disposed of as elemental sulfur by the Claus process. 2Claudio Bianchini was born in Reggello, Italy, in 1949. After receiving his Ph.D. degree in chemistry from the University of Florence in 1973, he joined the Chemistry Department as a bourse-holder . He then moved to the pharmaceutical industry A. Menarini in Florence (1976-77) as a research officer. At the end of 1977, he became a researcher at ISSECC-CNR. Currently he is the Executive Director of ISSECC-CNR. His main research interests are in the field of homogeneous and liquid biphase catalysis and organometallic chemistry.(1)Chart 1

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Section: Desulfurization Of Thiophenic Substrates To Hydrocarbons Wit...mentioning

confidence: 99%

Hydrogenation, Hydrogenolysis, and Desulfurization of Thiophenes by Soluble Metal Complexes: Recent Achievements and Future Directions

1998

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“…These thermodynamic isomers do not revert to the dicationic thiophene complexes upon treatment with acids, protonation occurs at carbon (27). Acylthiolato complexes derived from tetramethylthiophene thermally decompose to give tetramethylfuran and organometallic sulfido clusters (25).…”

Section: Base Hydrolysis and Ammonolysis Of Thiophene Complexesmentioning

confidence: 99%

Acid—Base Chemistry of Transition-Metal—π-Thiophene Complexes

Koczaja-Dailey

Luo

Rauchfuss

1996

ACS Symposium Series

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“…Cubane-type sulfido clusters in which each metal has an η 5 -C 5 R 5 coligand have been the subjects for the systematic investigation of the relationship between the number of the total electrons and the metal−metal interactions, ,,,− including the dynamics of the metal−metal bonds without changes in ancillary ligation. ,, Reactivities of these clusters, however, have been strictly limited to methylation of the bridging sulfur atoms as well as redox reactions owing to the robust M 4 (μ 3 -S) 4 cores surrounded by cyclopentadienyl ligands. In addition, most clusters of this type are homometallic; heterometallic cubane-type sulfido clusters with four cyclopentadienyl ligands remain less common. , Cluster 4 is notable in containing both electron-deficient group 4 metals and electron-rich group 8 metals in its cubane-type core.…”

Section: Introductionmentioning

confidence: 99%

Electron-Deficient Early−Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti₂Ru₂S₄ Cubane-Type Clusters with Four Cyclopentadienyl Coligands

1999

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Treatment of [Cp2Ti(SH)2] (1; Cp = η5-C5H5) with [(Cp*Ru)4(μ3-Cl)4] (2; Cp* = η5-C5Me5) in a Ti:Ru ratio of 1:1 afforded the hydrosulfido-bridged titanium−ruthenium heterobimetallic complex [Cp2Ti(μ2-SH)2RuClCp*] (3). Complex 3 reacted with an excess of triethylamine to give the early−late heterobimetallic cubane-type sulfido cluster [(CpTi)2(Cp*Ru)2(μ3-S)4] (4), with a loss of HCl and cyclopentadiene. An X-ray diffraction study and extended Hückel molecular orbital calculations for the 60e- cluster 4 demonstrated that 4 has four Ru→Ti dative bonds and a weak Ti−Ti interaction. The reaction of 4 with 3 equiv of [Cp2Fe][PF6] afforded the dicationic cubane-type cluster [(CpTi)2(Cp*Ru)2(μ3-S)4][PF6]2 (5), which contains an additional Ru−Ru bond. In contrast, oxidation of 4 with an excess of HCl at room temperature resulted in the formation of the neutral dichloride cluster [(CpTiCl2)(CpTi)(Cp*Ru)2(μ3-S)4] (6). Clusters 5 and 6 were converted into each other by treatment with chloride or hexafluorophosphate anion. Furthermore, substitution of one of the cyclopentadienyl ligands in 6 by a chloride anion took place in boiling 1,2-dichloroethane to give the trichloride cluster [(TiCl3)(CpTi)(Cp*Ru)2(μ3-S)4] (7). The detailed structures of these oxidized cubane-type clusters 5·2DMF, 6·CH2Cl2, and 7·CH2Cl2 as well as the hydrosulfido-bridged dinuclear complex 3 have also been determined by X-ray crystallography. The Ti2Ru2S4 cubane-type cores in 5−7 differ considerably in structure from each other, depending upon the ancillary ligands bound to the Ti atoms, although they have a Ru−Ru bond and two Ru→Ti dative bonds in common.

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Thermal Fragmentation of Acyl Thiolato Complexes to Reactive Metal Sulfido Intermediates. Structure of Ru(.eta.6-SC3Me3COMe)(PPh3)2

Cited by 20 publications

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Hydrogenation, Hydrogenolysis, and Desulfurization of Thiophenes by Soluble Metal Complexes: Recent Achievements and Future Directions

Hydrogenation, Hydrogenolysis, and Desulfurization of Thiophenes by Soluble Metal Complexes: Recent Achievements and Future Directions

Acid—Base Chemistry of Transition-Metal—π-Thiophene Complexes

Electron-Deficient Early−Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti₂Ru₂S₄ Cubane-Type Clusters with Four Cyclopentadienyl Coligands

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Thermal Fragmentation of Acyl Thiolato Complexes to Reactive Metal Sulfido Intermediates. Structure of Ru(.eta.6-SC3Me3COMe)(PPh3)2

Cited by 20 publications

References 0 publications

Hydrogenation, Hydrogenolysis, and Desulfurization of Thiophenes by Soluble Metal Complexes: Recent Achievements and Future Directions

Hydrogenation, Hydrogenolysis, and Desulfurization of Thiophenes by Soluble Metal Complexes: Recent Achievements and Future Directions

Acid—Base Chemistry of Transition-Metal—π-Thiophene Complexes

Electron-Deficient Early−Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti2Ru2S4 Cubane-Type Clusters with Four Cyclopentadienyl Coligands

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Electron-Deficient Early−Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti₂Ru₂S₄ Cubane-Type Clusters with Four Cyclopentadienyl Coligands