Carbon–sulfur bond cleavage of benzothiophene by Cp∗Co(C2H4)2

Chan, Natalie H.; Roache, James H.; Jones, William D.

doi:10.1016/j.ica.2015.07.040

Cited by 9 publications

(11 citation statements)

References 21 publications

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“…Cleavage of the C–S bonds of various sulfur substrates mediated by transition metals (e.g., Co, Fe, Ni, Cu, W, Rh, Ir, Ru, Os, Pd, and Pt), − in general, and Co(II), in particular, − , has been reported previously. Coordination of low-valent Mo with thiophenes, benzothiophenes, and selenophenes and subsequent C–S bond cleavage are also available in the literature. − ,, In most of these reports, only the C–S bonds of coordinated ligands were involved and the products were a result of metal insertion in the C–S bonds instead of complete removal of the −SH functionality from the organosulfur substrates.…”

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confidence: 60%

Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

et al. 2018

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Desulfurization of organosulfur compounds is a highly important reaction because of its relevance to the hydrodesulfurization (HDS) process of fossil fuels. A reaction system involving Co(BF)·6HO and the dinucleating ligands HBPMP or HPhBIMP has been developed that could desulfurize a large number of thiophenes, sulfides, and thiols to generate the complexes [Co(BPMP)(μ-SH)(MeCN)](BF) (1a), [Co(BPMP)(SH)](BF) (1b), and [Co(PhBIMP)(μ-SH)(X)](BF) [X = DMF (2a), MeCN (2c)], while the substrates are mostly converted to the corresponding alcohols/phenols. This convenient desulfurization process has been demonstrated for 25 substrates in 6 different solvents at room temperature.

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confidence: 60%

Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

et al. 2018

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“…The resulting purple slurry was then evaporated to dryness, the residue was extracted with CH 3 CN, and the extract was filtered. Et 2 O was then allowed to diffuse into the filtrate overnight at −35 °C with additional standing for 2 days at RT to afford the product as deep purple crystals (20 To a mixture of HPhBIMP (0.018 mmol, 21 mg) in 1 mL of DMF was added a solution of t BuS-SBu t (0.027 mmol, 4.87 mg) in 0.5 mL DMF, and the mixture was stirred for 5 min to give a yellow solution. A solution of Co(BF 4 ) 2 •6H 2 O (0.036 mmol, 12.4 mg) in 0.5 mL of DMF was added into the yellow solution, and the reaction mixture was stirred overnight.…”

Section: ■ Experimental Sectionmentioning

confidence: 92%

“…It is interesting to note that hydrosulfide units have been proposed to be involved in the HDS process. Moreover, transition-metal–hydrosulfide complexes have often been isolated as possible intermediates during the cleavage of C–S bonds in different transition-metal–thiolate complexes. − Consequently, transition-metal-mediated C–S bond cleavage of organosulfur substrates is being actively pursued by several research groups. − Along the same line, Ni(0)-mediated cleavage of C–S and S–S bonds of alkyl/aryl sulfoxides and disulfides, respectively, has been reported in the literature. The coordination of Mo with organosulfur compounds followed by C–S bond cleavage is also available in the literature. − However, most such reports involve the intramolecular C–S bond cleavage of coordinated ligands and metal insertion in C–S bonds, instead of a complete desulfurization of the substrate.…”

Section: Introductionmentioning

confidence: 99%

Comparative Study for the Cobalt(II)- and Iron(II)-Mediated Desulfurization of Disulfides Demonstrating That the C–S Bond Cleavage Step Precedes the S–S Bond Cleavage Step

Ganguly

Majumdar

2020

Inorg. Chem.

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A unique Co(II)-and Fe(II)-mediated complete desulfurization of disulfides of the type RS-SR and RC(O)S-SC(O)R to yield the corresponding alcohols (ROH) and carboxylic acids (RCOOH), respectively, along with the formation of a dicobalt(II)/diiron(II)− hydrosulfide complex, [M 2 (PhBIMP)(μ 2 -SH)(DMF)] 2+ (M = Co, Fe), has been demonstrated. This new desulfurization reaction involves cleavage of both C−S and S−S bonds, where the cleavage of the S−S bond (presumably two-electron reduction of the S−S bond) may generate two-electron-oxidized dicobalt(III)/diiron(III) species, [M III 2 (PhBIMP)(H 2 O) 2 (DMF) 2 ] 5+ (M = Co, Fe), in solution. While the generation of such a solvent-and/or H 2 O-coordinated dicobalt(III) species in the reaction solution could not be established beyond a doubt, formation of the diiron(III) species [Fe III 2 (PhBIMP)(H 2 O) 2 (DMF) 2 ] 5+ according to the proposed reaction mechanism has been confirmed by a combination of mass spectrometry and UV−vis spectroscopy in comparison with an authentic sample, synthesized directly by an independent procedure using Fe(ClO 4 ) 3 •xH 2 O. Interestingly, a comparative study using different types of disulfides and the molecular structure determination of a key reaction intermediate, [Fe 2 (PhBIMP)(MeCOSS)] 2+ , generated via the cleavage of only one C−S bond of MeC(O)S-SC(O)Me, demonstrates that the C−S bond cleavage step precedes the S−S bond cleavage step during the Fe(II)-mediated desulfurization of disulfides.

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“…The level of difficulty in removing sulfur by HDS reactions from organosulfur compounds found in crude oil generally increases in the order disulfides < alkyl mercaptans < aromatic mercaptans < diphenyl sulfide < thiophene, dibenzothiophene. , Interestingly, involvement of hydrosulfide units has been proposed in the HDS process and metal-hydrosulfide species have often been isolated as intermediates in the hydrogenolysis of C–S bonds in various thiolate ligated transition metal complexes. As a consequence, desulfurization of organosulfur substrates by various transition metals and possible formation of transition metal-hydrosulfide complexes are being actively pursued. − It may be noted that, while external stimuli mediated intramolecular C–S bond cleavage in a metal complex may give rise to ligand transformations and/or metallacycle formations, intermolecular C–S bond cleavage involving transition metals and externally added thiolates may allow access to new metal complexes featuring terminal or bridging hydrosulfides. Intermolecular C–S bond cleavage may have an added advantage in a sense that the identity of the ligand and hence the stability provided by the coordinating ligand to the metal complex will remain unchanged, and new, well-defined, metal complexes may thus be isolated based on the distribution of the −HS unit within the product.…”

Section: Introductionmentioning

confidence: 99%

Iron(II) Mediated Desulfurization of Organosulfur Substrates Produces Nonheme Diiron(II)-hydrosulfides

2019

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A reaction system involving Fe(BF4)2·6H2O and two dinucleating ligands, HBPMP and HPhBIMP, mediates the desulfurization of aliphatic and aromatic thiols at room temperature. This rare C–S bond cleavage reaction produces two nonheme diiron(II) complexes, [Fe2(BPMP)(SH)2(MeOH)2]1+ (1a) and [Fe2(PhBIMP)(μ-SH)(DMF)]2+ (2a), possibly via an active species similar to [Fe2(PhBIMP)(H2O)2(DMF)2]3+ (2c), while the thiols are converted to the corresponding alcohols/phenols. In the case of thioacetic acid, a bidentate chelating organosulfur substrate, the use of HBPMP produces the corresponding bis-thiocarboxylato bridged complex, [Fe2(BPMP)(CH3COS)2]1+ (1b), instead of 1a. However, the use of HPhBIMP allows the Fe(II) mediated desulfurization of thioacetic acid as well to yield 2a, along with the formation of [Fe2(PhBIMP)(CH3COS)(MeCN)]2+ (2b). This convenient desulfurization reaction has been demonstrated for different substrates in different solvents along with the structural and spectroscopic characterizations of the diiron(II)-hydrosulfide complexes in comparison with two isostructural chloride complexes, [Fe2(BPMP)(Cl)2(MeOH)2]1+ (1c) and [Fe2(PhBIMP)(μ-Cl)(DMF)]2+ (2d). The role of the individual reactants in the desulfurization process has been thoroughly investigated using control reactions, and on the basis of these results and the identification of intermediate species, such as [Fe2(PhBIMP)(S t Bu)(DMF)3]2+ and [Fe2(PhBIMP)(S t Bu)(H2O)(DMF)2]2+, in solution by mass spectrometry, a possible mechanism has been proposed.

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Carbon–sulfur bond cleavage of benzothiophene by Cp∗Co(C2H4)2

Cited by 9 publications

References 21 publications

Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

Comparative Study for the Cobalt(II)- and Iron(II)-Mediated Desulfurization of Disulfides Demonstrating That the C–S Bond Cleavage Step Precedes the S–S Bond Cleavage Step

Iron(II) Mediated Desulfurization of Organosulfur Substrates Produces Nonheme Diiron(II)-hydrosulfides

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